WO1998006728A1 - 2-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process - Google Patents

2-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process Download PDF

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Publication number
WO1998006728A1
WO1998006728A1 PCT/US1997/013171 US9713171W WO9806728A1 WO 1998006728 A1 WO1998006728 A1 WO 1998006728A1 US 9713171 W US9713171 W US 9713171W WO 9806728 A1 WO9806728 A1 WO 9806728A1
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Prior art keywords
metal complex
hydrocarbyl
inden
dimethyl
group
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PCT/US1997/013171
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French (fr)
Inventor
Jerzy Klosin
William J. Kruper, Jr.
Peter N. Nickias
Jasson T. Patton
David R. Wilson
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The Dow Chemical Company
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Priority to JP10509760A priority Critical patent/JP2000516608A/en
Priority to NZ333877A priority patent/NZ333877A/en
Priority to EP97937033A priority patent/EP1021454A1/en
Priority to HU9904148A priority patent/HUP9904148A3/en
Priority to CA002262377A priority patent/CA2262377A1/en
Priority to AU39647/97A priority patent/AU716659B2/en
Priority to BR9711115A priority patent/BR9711115A/en
Priority to SK152-99A priority patent/SK15299A3/en
Publication of WO1998006728A1 publication Critical patent/WO1998006728A1/en
Priority to NO990546A priority patent/NO990546L/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

  • This invention relates to a class of metal complexes, the ligands used to prepare these metal complexes and to olefin polymerization catalysts derived therefrom that are particularly suitable for use in a polymerization process for preparing polymers by polymerization ol ⁇ -olefins and mixtures of ⁇ -olefins
  • U S Patent No 's 5,350,817 and 5,304,614 disclose zirconium complexes with b ⁇ dged-metallocene ligands, wherein two indenyl groups are covalently linked together by a bridge containing carbon or silicon, which are useful for the polymerization of propylene
  • EP-A-577,581 discloses unsymmetrical bis-Cp metallocenes containing a fluorene ligand with heteroatom substituents E. Barsties; S. Schaible; M.-H. Prosenc; U. Rief; W. Roll, O. Weyland; B Dorerer; H.-H. B ⁇ ntzinger J Organometalhc Chem. 1996, 520, 63-68, and H. Plenio, D. birth J Organometalhc Chem.
  • Organometallics, 1992, 11, 21 15-2122 discloses Co-bridged bis-indenyl metallocenes with oxygen in the 5,6-pos ⁇ t ⁇ ons of the indenyl group, while N. Piccolravazzi, P Pino, G. Consigho; A Sironi, M. Moret Organometallics, 1990, 9, 3098-3105 discloses non-bridged bis-indenyl metallocenes with oxygen in the 4- and 7-pos ⁇ t ⁇ ons of the indenyl group.
  • M is a metal from one of Groups 3 to 13 of the Periodic Table of the
  • R independently each occurrence is hydrogen, or, is a group having from 1 to 80 nonhydrogen atoms which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl.
  • Z is a divalent moiety bound to both Cp and M via ⁇ -bonds, where Z comprises boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprises nitrogen, phosphorus, sulfur or oxygen,
  • X is an anionic or dianionic ligand group having up to 60 atoms exclusive of the class of ligands that are cyclic, delocalized, ⁇ -bound ligand groups,
  • X' independently each occurrence is a neutral Lewis base ligating compound having up to 20 atoms
  • p is zero, 1 or 2, and is two less than the formal oxidation state of M, when X is an anionic ligand, when X is a dianionic ligand group, p is 1 , and
  • the above complexes may exist as isolated crystals optionally in pure form or as a mixture with other complexes, in the form of a solvated adduct, optionally in a solvent, especially an organic liquid, as well as in the form of a dimer or chelated derivative thereof, wherein the chelating agent is an organic material, preferably a neutral Lewis base, especially a t ⁇ hydrocarbylamine, t ⁇ hydrocarbylphosphine, or halogenated derivative thereof
  • a catalyst system for olefin polymerization prepared from catalyst system components comprising (A) a catalyst component comprising a metal complex of one of the aforementioned complexes, and
  • (B) a cocatalyst component comprising an activating cocatalyst wherein the molar ratio of (A) to (B) is from 1 10,000 to 100 1 , or activation of (A) by use of an activating technique
  • (B) a cocatalyst component comprising an activating cocatalyst wherein the molar ratio of (A) to (B) is from I 10,000 to 100 1
  • the metal complex is in the form of a radical cation
  • a preferred process of this invention is a high temperature solution polymerization process for the polymerization of olefins comprising contacting one or more C2-20 ⁇ -olefins under polymerization conditions with one of the aforementioned catalyst systems at a temperature from about 100°C to about 250°C
  • This invention also provides a cyclopentadienyl-containing ligand of one of the aforementioned metal complexes where the ligand is in the form of
  • the present catalysts and processes result in the highly efficient production of high molecular weight olefin polymers over a wide range of polymerization conditions, and especially at elevated temperatures They are especially useful tor the solution or bulk polymerization of ethylene/propylene (EP polymers), ethylene/octene (EO polymers), cthylene/styrene (ES polymers), propylene and ethylene/propylene/diene (EPDM polymers) wherein the diene is ethylidenenorbomene, 1 ,4-hexad ⁇ ene or similar nonconjugated dienc
  • EP polymers ethylene/propylene
  • EO polymers ethylene/octene
  • ES polymers cthylene/styrene
  • EPDM polymers ethylene/propylene/diene
  • the diene is ethylidenenorbomene, 1 ,4-hexad ⁇ ene or similar nonconjugated dienc
  • the catalysts of this invention may also be supported on a support material and used in olefin polymerization processes in a slurry or in the gas phase
  • the catalyst may be prepolyme ⁇ zed with one or more olefin monomers in situ in a polymerization reactor or in a separate process with intermediate recovery of the prepolyme ⁇ zed catalyst prior to the primary polymerization process
  • Figure 1 shows the crystal structure of d ⁇ chloro(N-( l , l-d ⁇ methylethyl)-l, l- dimethyl- 1 -(( 1.2.3,3a,7a- ⁇ )-2-d ⁇ methylam ⁇ no- 1 H-inden- 1 -y l)s ⁇ lanam ⁇ nato-(2-)-N-)- titanium.
  • Figure 2 shows the crystal structure of (N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1- (( 1 ,2,3.3a,7a- ⁇ )-2-ethoxy- 1 H-inden- 1 -yl)s ⁇ lanam ⁇ nato-(2-)-N-)-d ⁇ methyl-t ⁇ tan ⁇ um.
  • Olefins as used herein are C2-20 aliphatic or aromatic compounds containing vinylic unsaturation, as well as cyclic compounds such as cyclobutene, cyclopentene, and norbornene, including norbornene substituted in the 5- and 6- positions with C l-20 hydrocarbyl groups Also included are mixtures of such olefins as well as mixtures of such olefins with C4.40 diolefin compounds Examples of the latter compounds include ethy dene norbornene, 1 ,4-hexad ⁇ ene, norbornadiene, and the like.
  • the catalysts and processes herein are especially suited for use in preparation of ethylene/1 -butene, ethylene/1 -hexene, ethylene/styrene, ethylene/propylene, ethylene/1 -pentene, ethylene/4-methyl-l-pentene and ethylene/1-octene copolymers as well as terpolymers of ethylene, propylene and a nonconjugated diene, such as, for example, EPDM terpolymers
  • Preferred X' groups are carbon monoxide, phosphines, especially t ⁇ methylphosphine, t ⁇ ethylphosphine, t ⁇ phenylphosphine and b ⁇ s(l ,2- d ⁇ methylphosph ⁇ no)ethane, P(OR')3, wherein R 1 is hydrocarbyl, silyl or a combination thereof, ethers, especially tetrahydrofuran, amines, especially py ⁇ dine, bipy ⁇ dine, tetramethylethylenediamine (TMEDA), and triethylamine, olefins, and conjugated dienes having from 4 to 40 carbon atoms Complexes including the latter X' groups include those wherein the metal is in the +2 formal oxidation state
  • Preferred coordination complexes according to the present invention are complexes corresponding to the formula
  • R ⁇ , R ⁇ R * and R ⁇ are R groups, each of which independently is hydrogen, or is a group having from 1 to 80 nonhydrogen atoms which is hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl, hydrocarbylsilylhydrocarbyl, each of R ⁇ , R ⁇ , R ⁇ and R ⁇ optionally being substituted with one or more groups which independently each occurrence is hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, d ⁇ (hydrocarbyls ⁇ lyl)am ⁇ no, hydrocarbylamino, d ⁇ (hydrocarbyl)am ⁇ no, d ⁇ (hydrocarbyl)phosph ⁇ no, hydrocarbylsulfido, hydrocarbyl, halo-substituted hydrocarbyl,
  • R ⁇ , R ⁇ , R A and R B are covalently linked with each other to form one or more fused rings or ring systems having from 1 to 80 nonhydrogen atoms for each R group, the one or more fused rings or ring systems being unsubstituted or substituted with one or more groups which are hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino.
  • R ⁇ groups are those wherein R A IS hydrocarbyl, hydrocarbylsilyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl and T is O or N, more preferred are those wherein R A u, hydrocarbyl or hydrocarbylsilyl and T is O or N, and still more preferred are wherein RA IS hydrocarbyl or hydrocarbylsilyl and T is O
  • Preferred heteroatom-containing substituents at the 2-pos ⁇ t ⁇ on of the Cp are those wherein the (R A ),-T group dimethylamino, diethylamino, methylethylamino, methylphenylammo, dipropylamino, dibutylammo, pipe ⁇ dinyl, morpholinyl, pyrro dinyl, hexahydro-l H-azepin- l-yl, hexahydro-l(2H)-azoc ⁇ nyl, octahydro- 1 H- azon ⁇ n- 1-yl, octahydro- l(2H)-azec ⁇ nyl, methoxy, ethoxy, propoxy, methylethyloxy, 1 , 1-d ⁇ methyethyloxy, t ⁇ methylsiloxy or l , l-d ⁇ methylethyl(d ⁇ methyls ⁇ lyl)oxy
  • (RA).-T group is methoxy, ethoxy, propoxy, methylethyloxy, 1 , 1-d ⁇ methyethyloxy, t ⁇ methylsiloxy, 1 , 1 - d ⁇ methylethyl(d ⁇ methyls ⁇ lyl)oxy
  • either the ligand or metal complex has one or more fused rings or ring systems in addition to the Cp or indenyl wherein the one or more fused rings or ring systems contain one or more ring heteroatoms which are N, O. S, or P Preferred ring heteroatoms are N or O, with N being more highly preferred.
  • metal complexes and the heteroatom-containing ligands thereof where -Z- is -Z*-Y-, with Z* bonded to Cp and Y bonded to M, and
  • Y is -O-, -S-, -NR*-, -PR*-,
  • R* independently each occurrence is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R* having up to 20 nonhydrogen atoms, and optionally, two R* groups from Z (when R* is not hydrogen), or an R* group from Z and an R* group from Y form a ring system,
  • X is independently each occurrence methyl, benzyl, t ⁇ methylsilylmethyl, allyl, pyrollyl or two X groups together are 1 ,4-butane-d ⁇ yl, 2-butene- 1 ,4-d ⁇ yl, 2,3-d ⁇ methyl-2-butene- 1 ,4-d ⁇ yl, 2-methyl-2-butene-l ,4-d ⁇ yl, or xylyldiyl
  • metal complexes and the heteroatom-containing ligands thereof where -Z- is -Z*-Y-, with Z* bonded to Cp and Y bonded to M, and
  • Y is -O-, -S-, -NR*-, -PR*-,
  • R* independently each occurrence is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R* having up to 20 nonhydrogen atoms, and optionally, two R* groups from Z (when R* is not hydrogen), or an R* group from Z and an R x group from Y form a ring system,
  • metal complexes and the heteroatom-containing ligands thereof where -Z- is -Z*-Y-, with Z* bonded to Cp and Y bonded to M.
  • Y is -O-, -S-, -NR*-, -PR*-
  • R* independently each occurrence is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R* having up to 20 nonhydrogen atoms, and optionally, two R* groups from Z (when R* is not hydrogen), or an R* group from Z and an R* group from Y form a ring system;
  • metals can be used in the preparation of the metal complexes of this invention, desirably a metal from one of Groups 3 to 13 of the Periodic Table of the Elements, the lanthanides or actinides, which is in the +2, +3 or +4 formal oxidation state, more desirably a metal from one of Groups 3 to 13
  • Metal complexes of this invention having somewhat different characteristics are those where M is a metal from one of Groups 3-6, one of Groups 7-9 or one of Groups 10-12. Preferred are those where M is a metal from Group 4, desirably Ti, Zr or Hf, with Ti and Zr being more preferred.
  • Ti is the most highly preferred metal, especially for use in complexes which contain only one Cp-contaming ligand which is the heteratom- containing ligand of this invention, while Zr is highly preferred for use in complexes which contain two Cp-containmg ligands, at least one of which is a heteratom- containing ligand.
  • Ti is in the +4 formal oxidation state, while, alternatively it is preferred that Ti is in the +3 formal oxidation state, and more preferred is that Ti is in the +2 formal oxidation state
  • Zr is in the +4 formal oxidation state, or, alternatively, in the +2 formal oxidation state
  • Y is -NR ⁇ with the more preferred -NR* being those where R* is a group having a primary or secondary carbon atom bonded to N Highly preferred are those where R* is cyclohexyl oi isopropyl
  • the complexes can be prepared by use of well known synthetic techniques
  • a reducing agent can be employed to produce the lower oxidation state complexes
  • a suitable noninterfe ⁇ ng solvent at a temperature from -100 to 300°C, preferably from -78 to 100°C, most preferably from 0 to 50°C
  • reducing agent herein is meant a metal or compound which, under reducing conditions causes the metal M, to be reduced from a higher to a lowei oxidation state
  • suitable metal reducing agents are alkali metals, alkaline earth metals, aluminum and zinc, alloys of alkali metals or alkaline earth metals such as sodium/mercury amalgam and sodium/potassium alloy
  • suitable reducing agent compounds are sodium naphthalenide, potassium graphite, lithium alkyls, lithium or potassium
  • Suitable reaction media for the formation of the complexes include aliphatic and aromatic hydrocarbons, ethers, and cyclic ethers, particularly branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, aromatic and hydrocarbyl-substituted aromatic compounds such as benzene, toluene, and xylene, C [_4 dialkyl ethers, C j _4 dialkyl ether derivatives of (poly)alkylene glycols, and tetrahydrofuran. Mixtures of the foregoing are also suitable
  • R, R' , R", R" ⁇ R"" independently selected in each case are H (except on the nitrogen bound directly to the cyclopentadienyl ring), alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, and are not limited only to these groups
  • the heteroatom-containing substituent has a nitrogen in the 2-pos ⁇ t ⁇ on of the indenyl system.
  • 2-Indanone is a convenient starting material for conversion to the corresponding enamine, although formation of the latter is not restricted to the use of this compound.
  • Enamines of indanone are typically formed by methods known in the art, including condensation of secondary amines with the ketone in anhydrous alcohol (U. Edlund Acta Chemica Scandinavica, 1974, 27, 4027-4029).
  • enamines of 2- ⁇ ndanone are more easily formed by amine condensation than 1 -indanone analogues.
  • ste ⁇ cally hindered ketones such as l -methyl-2- ⁇ ndanone or more volatile amines such as dimethyl amine
  • dehydrating reagents such as titanium chloroamides (generated in situ from titanium tetrachlo ⁇ de and the condensation amine) (R. Carlson, A Nilsson Acta Chemica Scandinavica B 38, 1984, 49-53).
  • titanium chloroamides generated in situ from titanium tetrachlo ⁇ de and the condensation amine
  • R. Carlson A Nilsson Acta Chemica Scandinavica B 38, 1984, 49-53
  • These two methods have been employed to produce enamines substituted in the 2-pos ⁇ t ⁇ on of the indene (the 1 -position is typically bonded to a silicon or other linking moiety in subsequent compounds).
  • Another method for the preparation of enamines involves electrophilic amination of carbanions such as lithium indenide (E. Erdik, M, Ay Chem Rev.. 1989
  • enamines prepared by these routes must be highly pure and free of ketone, Aldol by-products and higher weight reaction tars which typically accompany product formation. None of the aforementioned routes uniformly provides a product which can be used without some sort of further purification
  • chromatographic purification using flash-grade silica gel or alumina rapidly promotes hydrolysis of the enamine to free amine and ketone, an unfortunate consequence.
  • enamines of this nature may be purified by careful fractional distillation, or occasionally, recrystallization. In particular, rapid distillation of indanone enamines is required to prevent thermal polymerization in the still at elevated temperature.
  • R, R', R", R'", R" independently selected in each case are H (except on oxygen), alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, and are not limited only to these groups.
  • enol ethers in this position can be made by dehydration of the appropriate hemiketal which is formed in situ from indanone and alcohol in theistnce of an acidic catalyst (L A Paquette, A Varadarajan, E Bey J Am Chem Soc 1984, 106, 6702-6708, W E Parham, C D Wright J Org Chem 1957, 22, 1473-77)
  • Silyl enol ethers can be made by forming the enolate of 2- ⁇ ndanone and quenching with, for example, t-butyl-dimethylsilyl chloride (R Leino, H Luttikhedde C E Wilen, R Sillanpa, J H Nasman, Organometallics, 1996, 15, 2450-2453)
  • Enol ethers of indanones like the enamine analogues, are also susceptible to hydrolysis and are very oxygen sensitive Once purified, they are best expediently converted to their corresponding
  • conversion of the enamine to its corresponding anionic salt may be accomplished by reaction with an appropriate base of suitable strength in an appropriate noninteife ⁇ ng solvent Under appropriate, anaerobic, anhydrous conditions, the often solid anionic salt may be filtered, washed and dried in nearly quantitative yield Likewise, enol ethers of 2- ⁇ ndanone can be deprotonated to the corresponding anionic salt
  • suitable base is more restricted in the case of silyl enol ethers, since certain bases, like n-butyllithium, were found to cause desilylation with generation of the enolate anion (base attack on the silyl group)
  • CGC-ligand constrained geometry ligands
  • a cyclopentadienyl anion is reacted with electrophiles such as halogenated secondary alkylamines or halogenated secondary silylamines to give the corresponding cyclopentadienyl alkylamine or cyclopentadienyl silylamme
  • electrophiles such as halogenated secondary alkylamines or halogenated secondary silylamines
  • solvents suitable for the preparation of the anionic salts and dianionic salts of the invention include, but are not limited to aliphatic and aromatic hydrocarbons, particularly straight and branched chain hydrocarbons such as butane, pentane, hexane, heptane, octane, decane, including their branched isomers and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyciohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; aromatic and hydrocarbyl-substituted aromatic compounds such as benzene, toluene, xylene, ethylbenzene, diethylbenzene and mixtures thereof; ethers and cyclic ethers
  • Bases of suitable strength for the preparation of the dianionic salts of the invention include hydrocarbyl salts of Group 1 and Group 2 metals, especially alkyl or aryl salts of lithium or magnesium, such as methyllithium, ethyllithium, n- butyllithium, s-butyllithium, t-butyllithium, phenyllithium, methyl magnesium chloride, ethyl magnesium bromide, i-propyl magnesium chloride, dibutylmagnesium, (butyl)(ethyl)magnesium, dihexylmagnesium; Group 1 or Group 2 metals, such as lithium, sodium, potassium and magnesium; Group 1, Group 2 or Group 13 metal hydrides, such as lithium hydride, sodium hydride, potassium hydride or lithium aluminum hydride.
  • Group 1 or Group 2 metal amide complexes such as lithium diisopropylamidc, lithium dimethylamide, lithium hexamethyldisilazide, so
  • Bases of suitable strength for the preparation of the anionic salts of the invention include the foregoing as well as Group 1 or Group 2 metal alkoxide complexes, such as sodium ethoxide, sodium t- butoxide, potassium butoxide and potassium amylate
  • the metallation of the dianionic salt may be accomplished by methods cited in this art as well. Reaction of the dianionic salt in THF with TiCl 3 (THF followed by oxidation with methylene chloride or lead dichlo ⁇ de is a well established procedure (J. Okuda, S. Verch, T. P. Spaniol, R. Stur er Chem. Ber., 1996, 129, 1429- 1431, D. D Devore EP 514,828) which affords the titanium (IV) dichlo ⁇ de complex.
  • the dichlo ⁇ de may be silylated or hydrocarbylated by ligand exchange with an appropriate silylating or hydrocarbylating agent, such as methyllithium, methyl magnesium chloride, benzyl potassium, allyl lithium, t ⁇ methyisilylmethyl lithium, neopentyl magnesium bromide and phenylhthium.
  • an appropriate silylating or hydrocarbylating agent such as methyllithium, methyl magnesium chloride, benzyl potassium, allyl lithium, t ⁇ methyisilylmethyl lithium, neopentyl magnesium bromide and phenylhthium.
  • the formation of the CGC metal (III) complexes according to the invention can be accomplished by any of several synthesis methods, among which are the following:
  • the reaction under anaerobic and anhydrous conditions of the dianionic salts with t ⁇ valent metal salts, such as Group 4 metal (III) halide or alkoxide complexes can be carried out, optionally followed by silylation or hydrocarbylation with suitable silylating or hydrocarbylating agents, to form the corresponding CGC metal (III) halide, alkoxide, silyl or hydrocarbyl complexes of the invention
  • a further synthesis method involves reducing an appropriate CGC metal (IV) dihahde or dialkoxide complex, or, preceded by monosilylation or monohydrocarbylation, the corresponding CGC (IV) silyl or hydrocarbyl monohalide or monoalkoxide complex with a suitable reducing agent to the corresponding CGC metal (III) halide, alkoxide, silyl or hydrocarbyl complex
  • CGC metal (III) complexes are the methods described by Wilson (D R Wilson US 5,504,224, 1996) which is incorporated herein by reference
  • cyclopentadienyl ligands can be displaced by the dianionic salts and/or by the (stabilizing) hydrocarbylating agents from cyclopentadienyl-containing Group 4 metal complexes m the +3 oxidation state to give the CGC metal (III) complexes of the invention
  • Suitable reducing agents for reducing the oxidation state of the metals of the CGC metal (IV) complexes from +4 to +3 have been described above and especially include zinc, aluminum and magnesium
  • Suitable silylating and hydrocarbylating agents for the CGC metal (III) complexes and the CGC metal (IV) complexes of the invention include alkyl, such as methyl, ethyl, propyl, butyl, neopentyl and hexyl, aryl, such as phenyl, naphthyl and biphenyl, aralkyl, such as benzyl, tolylmethyl, diphenylmethyl; alkaryl, such as tolyl and xylyl, allyl, silyl- or alkyl-substituted allyl, such as methylallyl, t ⁇ methylsilylallyl, dimethylallyl and t ⁇ methylallyl, t ⁇ alkylsilyl, such as t ⁇ methylsilyl and t ⁇ ethylsilyl, t ⁇ alkylsilylalkyl, such as t ⁇ methylsilylmethyl, pentadienyl, alky
  • dialkylaminoalkaryl such as o-(N,N- dimethylaminomethyOphenyl
  • dialkylammoaralkyl such as o-(N,N- dimethylamino)benzyl
  • salts of Group 1 , 2 or 13 metals preferably the salts of lithium, sodium, potassium, magnesium and aluminum.
  • Preferred silylating and hydrocarbylating agents include trimethylaluminum, methyllithium, methyl magnesium chloride, neopentyllithium, trimethylsilylmethyi magnesium chloride and phenyllithium.
  • Stabilizing group-containing hydrocarbylating agents are also included, especially the stabilizing group-containing hydrocarbylating agents and salts of the stabilizing group-containing hydrocarbyl groups described in US 5,504,224, whose salts include, for example, benzyl potassium, 2-(N,N-dimethylamino)benzyllithium, allyllithium and dimethylpentadienyl potassium.
  • the stabilizing groups are further described in U.S. Ser. No. 8003, filed Jan. 21 , 1993 (corresponding to WO 93/19104), incorporated herein by reference.
  • Preferred halides or alkoxides of the metal (III) halide or alkoxide complexes and the CGC metal (III) halide or alkoxide complexes include fluoride, chloride, bromide, iodide, methoxide, ethoxide, i-propoxide, n- propoxide, butoxide and phenoxide.
  • Preferred metal (III) halide or alkoxide complexes include titanium (III) chloride, titanium (III) ethoxide, titanium (III) bromide, titanium (III) isopropoxide, titanium (III) (dichloro)(isopropoxide), as well as Lewis base complexes of the foregoing, especially ether complexes thereof, particularly diethyl ether, tetrahydrofuran and ethylene glycol dimethyl ether complexes thereof.
  • Preferred cyclopentadienyl-containing Group 4 metal complexes in the +3 oxidation state include triscyclopentadienyl titanium, biscyclopentadienyl titanium chloride, biscyclopentadienyl titanium bromide, biscyclopentadienyl titanium isopropoxide, cyclopentadienyl titanium dichloride, cyclopentadienyl titanium diphenoxide, cyclopentadienyl titanium dimethoxide and bis((trimethylsilyl)(t- butyl )cyclopentadienyl)zirconium chloride.
  • the ligands of this invention are 2-heteroatom substituted cyclopentadienyl- containing ligands where the ligand is in the form of:
  • a ligand of this invention for synthesis to produce a metal complex of this invention, or for synthesis to produce a metal complex comprising a metal from one of Groups 3 to 13 of the Periodic Table of the Elements, the ianthanides or actinides, and from 1 to 4 of the ligands.
  • the ligands of this invention may be used in various forms, including salts, with various groups attached at the Z position in syntheses leading to metal complexes in which the metal is from Groups 3-16 of periodic table or the Ianthanides, and in which from one to four of these ligands, alone or in combination with other ligands, are present in the metal complex.
  • the methods of synthesis may be similar or analogous to those discussed herein for the Group 4 metal complexes of this invention, as well as various other synthetic procedures known in the art.
  • the metal complexes are useful as catalysts in various reactions, including olefin polymerization reactions.
  • x is 0 or 1
  • y is 0 or 1
  • z is 0 or 1
  • x + y is 0 or 1
  • x + z is 0 or 1
  • the other symbols are as previously defined, where the dotted circle within the Cp ring implies the various possibilities for double bond character, partial double bond character or aromatic character as appropriate, depending upon the values for x, y, and z
  • the complexes are rendered catalytically active by combination with an activating cocatalyst or by use of an activating technique.
  • Suitable activating cocatalysts for use herein include polymeric or oligomeric alumoxanes, especially methylalumoxane, t ⁇ isobutyl aluminum modified methylalumoxane, or lsobutytalumoxane; neutral Lewis acids, such as C 1.45 hydrocarbyl substituted Group
  • Combinations of neutral Lewis acids especially the combination of a t ⁇ alkyl aluminum compound having from 1 to 4 carbons in each alkyl group and a halogenated t ⁇ (hydrocarbyl)boron compound having from 1 to 20 carbons in each hydrocarbyl group, especially t ⁇ s(pentafluorophenyl)borane, t ⁇ s(o- nonafluorobiphenyOborane, further combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially t ⁇ s(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane are especially desirable activating cocatalysts
  • a benefit according to the present invention is the discovery that the most efficient catalyst activation using such a combination of t ⁇ s(pentafluorophenyl)borane/alumoxane mixture occurs at reduced levels of alumoxan
  • Suitable ion forming compounds useful as cocatalysts in one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and a compatible, noncoordinating anion,
  • noncoordinating means an anion or substance which either does not coordinate to the Group 4 metal containing precursor complex and the catalytic derivative derived therefrom, or which is only weakly coordinated to such complexes thereby remaining sufficiently labile to be displaced by a neutral Lewis base
  • a noncoordinating anion specifically refers to an anion which when functioning as a charge balancing anion in a cationic metal complex does not transfer an anionic substituent or fragment thereof to said cation thereby forming neutral complexes
  • “Compatible anions” are anions which are not degraded to neutrality when the initially formed complex decomposes and are noninterfe ⁇ ng with desired subsequent polymerization or other uses of the complex
  • Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of the active catalyst species (the metal cation) which may be formed when the two components are combined Also, said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nit ⁇ les.
  • Suitable metals include, but are not limited to, aluminum, gold and platinum.
  • Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon.
  • Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom arc, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially
  • cocatalysts may be represented by the following general formula
  • L* is a neutral Lewis base
  • (L*-H)+ is a Bronsted acid
  • ( )d- is a noncoordinating, compatible anion having a charge of d-
  • d is an integer from 1 to 3
  • (A)d- corresponds to the formula. [MO4] ,
  • M' is boron or aluminum in the +3 formal oxidation state
  • Q independently each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halosubstituted-hydrocarbyl, halosubstituted hydrocarbyloxy, and halo- substituted silylhydrocarbyl radicals (including perhalogenated hydrocarbyl- perhalogenated hydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Q having up to 20 carbons with the proviso that in not more than one occurrence is Q halide.
  • suitable hydrocarbyloxide Q groups are disclosed in U.S. Patent 5,296,433, the teachings of which are herein incorporated by reference.
  • d is one, that is, the counter ion has a single negative charge and is A " .
  • Activating cocatalysts comprising boron which are particularly useful in the preparation of catalysts of this invention may be represented by the following general formula:
  • B is boron in a formal oxidation state of 3
  • Q is a hydrocarbyl-, hydrocarbyloxy-, fluo ⁇ nated hydrocarbyl-, fluo ⁇ nated hydrocarbyloxy-, or fluo ⁇ nated silylhydrocarbyl- group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl.
  • Q is each occurrence a fluo ⁇ nated aryl group, especially, a pentafluorophenyl group.
  • Illustrative, but not limiting, examples of ion forming compounds comprising proton donatable cations which may be used as activating cocatalysts in the preparation of the catalysts of this invention are t ⁇ -substituted ammonium salts such as: t ⁇ methylammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, t ⁇ ethylammonium tetraphenylborate, t ⁇ propylammonium tetraphenylborate, t ⁇ (n-butyl)ammon ⁇ um tetraphenylborate, methyltetradecyloctadecylammonium tetraphenylborate,
  • Dialkyl ammonium salts such as d ⁇ -( ⁇ -propy ] )ammon ⁇ um tetrak ⁇ s(pentafluorophenyl)borate, and dicyclohexylammonium tetrak ⁇ s(pentafluorophenyl)borate
  • T ⁇ -substituted phosphonium salts such as triphenylphosphonium tetrak ⁇ s(pentafluorophenyl)borate, t ⁇ (o-tolyl)phosphon ⁇ um tetrak ⁇ s(pentafluorophenyl)borate, and t ⁇ (2 6-d ⁇ methylphenyl)phosphon ⁇ um tetrak ⁇ s(pentafluorophenyl)borate
  • An especially preferred group of activating cocatalysts is t ⁇ s(pentafluorophenyl)borane, N-R3.N-R4 anilinium tetrak ⁇ s(pentafluorophenyI)borate where R3 and R4 independently each occurrence are substituted or unsubstituted saturated hydrocarbyl groups having from 1 to 8 carbon atoms, (R ⁇ R2NHCH3) + (C 6 H 4 OH)B(C 6 F 5 ) 3 , or (R 1 R 2 NHCH 3 ) + B(C 6 F 5 ) 4 , where R ⁇ and R 2 independently each occurrence are substituted or unsubstituted saturated hydrocarbyl groups having from 12 to 30 carbon atoms
  • Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula
  • Ox e+ is a cationic oxidizing agent having a charge of e+, e is an integer from 1 to 3, and A 0" - and d are as previously defined
  • cationic oxidizing agents include: ferrocenium, hydrocarbyl- substituted ferrocenium, Ag + ' or Pb + 2
  • Preferred embodiments of A ⁇ " are those anions previously defined with respect to the Bronsted acid containing activating cocatalysts, especially tetrak ⁇ s(pentafluorophenyl)borate.
  • Another suitable ion forming, activating cocatalyst comprises a compound which is a salt of a carbenium ion and a noncoordinating, compatible anion represented by the formula.
  • ⁇ + is a C ] _20 carbenium ion
  • a " is as previously defined
  • a preferred carbenium ion is the t ⁇ tyl cation, i.e triphenyl methy hum
  • a further suitable ion forming, activating cocatalyst comprises a compound which is a salt of a silylium ion and a noncoordinating, compatible anion represented by the formula
  • R is C ] _ ⁇ o hydrocarbyl, and X', q and A " aie as previously defined.
  • Preferred silylium salt activating cocatalysts are t ⁇ methylsilylium tetrakispentafluorophenylborate, t ⁇ ethylsilylium tetrakispentafluorophenylborate and ether substituted adducts thereof.
  • Silylium salts have been previously gene ⁇ cally disclosed in J Chem Soc Chem Comm., 1993, 383-384, as well as Lambert, J B , et al , Organometallics, 1994, 13, 2430-2443
  • the use of the above silylium salts as activating cocatalysts for addition polymerization catalysts is claimed in United States Patent Application entitled, "Silylium Cationic Polymerization Activators For Metallocene Complexes", filed in the names of David Neithamer, David Devore, Robert LaPointe and Robert Mussell on September 12, 1994
  • the technique of bulk electrolysis involves the electrochemical oxidation of the metal complex under electrolysis conditions in the presence of a supporting electrolyte comprising a noncoordinating, inert anion.
  • solvents, supporting electrolytes and electrolytic potentials for the electrolysis are used such that electrolysis byproducts that would render the metal complex catalytically inactive are not substantially formed during the reaction
  • suitable solvents are materials that are liquids under the conditions of the electrolysis (generally temperatures from 0 to 100°C), capable of dissolving the supporting electrolyte, and inert "Inert solvents" are those that are not reduced or oxidized under the reaction conditions employed for the electrolysis It is generally possible in view of the desired electrolysis reaction to choose a solvent and a supporting electrolyte that are unaffected by the electrical potential used for the desired electrolysis
  • Preferred solvents include difluorobenzene (all isomers), dimethoxyethane (DME), and mixtures thereof
  • the electrolysis may be conducted in a standard electrolytic cell containing an anode and cathode (also referred to as the working electrode and counter electrode respectively) Suitable materials of construction for the cell are glass, plastic, ceramic and glass coated metal
  • the electrodes are prepared from inert conductive materials, by which are meant conductive materials that are unaffected by the reaction mixture or reaction conditions Platinum or palladium are preferred inert conductive materials Normally an ion permeable membrane such as a fine glass frit separates the cell into separate compartments, the working electrode compartment and counter electrode compartment
  • the working electrode is immersed in a reaction medium comprising the metal complex to be activated, solvent, supporting electrolyte, and any other materials desired for moderating the electrolysis or stabilizing the resulting complex
  • the counter electrode is immersed in a mixture of the solvent and supporting electrolyte
  • the desired voltage may be determined by theoretical calculations or experimentally by sweeping the cell using a reference electrode such as a silver electrode immersed in the cell electrolyte
  • Suitable supporting electrolytes are salts comprising a cation and a compatible, noncoordinating anion,
  • A- Preferred supporting electrolytes are salts corresponding to the formula G + A ; wherein.
  • G + is a cation which is nonreactive towards the starting and resulting complex
  • A" is as previously defined.
  • Examples of cations, G + include tetrahydrocarbyl substituted ammonium or phosphonium cations having up to 40 nonhydrogen atoms.
  • Preferred cations are the tetra(n-butylammon ⁇ um)- and tetraethylammonium- cations
  • the cation of the supporting electrolyte passes to the counter electrode and A" migrates to the working electrode to become the anion of the resulting oxidized product.
  • Either the solvent or the cation of the supporting electrolyte is reduced at the counter electrode in equal molar quantity with the amount of oxidized metal complex formed at the working electrode.
  • Preferred supporting electrolytes are tetrahydrocarbylammonium salts of tetrak ⁇ s(perfluoroaryl) borates having from 1 to 10 carbons in each hydrocarbyl or perfluoroaryl group, especially tetra(n- butylammon ⁇ um)tetrakis(pentafluorophenyl) borate.
  • a further recently discovered electrochemical technique for generation of activating cocatalysts is the electrolysis of a disilane compound in the presence of a source of a noncoordinating compatible anion.
  • This technique is more fully disclosed and claimed in the previously mentioned United States Patent application entitled, "Silylium Cationic Polymerization Activators For Metallocene Complexes", filed on September 12, 1994.
  • the foregoing electrochemical activating technique and activating cocatalysts may also be used in combination
  • An especially preferred combination is a mixture of a t ⁇ (hydrocarbyl)alum ⁇ num or t ⁇ (hydrocarbyl)borane compound having from 1 to 4 carbons in each hydrocarbyl group with an oligomeric or polymeric alumoxane compound
  • the molar ratio of catalyst/cocatalyst employed preferably ranges from 1 10,000 to 100 1 , more preferably from 1 -5000 to 10 1 , most preferably from 1 1000 to 1 1
  • Alumoxane, when used by itself as an activating cocatalyst, is employed in large quantity, generally at least 100 times the quantity of metal complex on a molar basis T ⁇ s(pentafluorophenyl)borane, where used as an activating cocatalyst, is employed in a molar ratio to the metal complex of form 0 5 1 to 10 1 , more preferably from 1 I to 6' 1 , most preferably from 1 1 to 5 1
  • the remaining activating cocatalysts are generally employed in approximately equimolar quantity with the metal complex
  • the process may be used to polymerize ethylenically unsaturated monomers having from 2 to 20 carbon atoms either alone or in combination
  • Preferred monomers include monoviny dene aromatic monomers, especially styrene, 4-v ⁇ nylcyclohexene, vinylcyclohexane, norbornadiene and C2- ] ⁇ aliphatic ⁇ -olefins, especially ethylene, propylene, isobutylene, 1 -butene, 1 -pentene, 1 -hexene, 3-methyl- l-pentene, 4-methyl- 1-pentene, 1 -heptene, and 1-octene, C4.40 dienes, and mixtures thereof
  • Most preferred monomers are ethylene, propylene, 1 -butene, 1 -hexene, 1 -octene nd mixtures of ethylene, propylene and a nonconjugated diene, especially ethylidenenorbo
  • the polymerization may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that is, temperatures from 0-250°C, preferably 30 to 200°C and pressures from atmospheric to 10,000 atmospheres Suspension, solution, slurry, gas phase, bulk, solid state powder polymerization or other process condition may be employed if desired
  • a support, especially silica, alumina, or a polymer (especially poly(tetrafluoroethylene) or a polyolefin) may be employed, and desirably is employed when the catalysts are used in a gas phase or slurry polymerization process.
  • the support is preferably employed in an amount to provide a weight ratio of catalyst (based on metal):support from 1 : 100,000 to 1.10, more preferably from 1 :50,000 to 1 :20, and most preferably from 1 - 10,000 to 1 :30.
  • One such polymerization process comprises contacting, optionally in a solvent, one or more ⁇ -olefins with a catalyst according to the present invention, in one or more continuous stirred tank or tubular reactors, connected in series or parallel, or in the absence of solvent, optionally in a fluidized bed gas phase reactor, and recovering the resulting polymer. Condensed monomer or solvent may be added to the gas phase reactor as is well known in the art.
  • the molar ratio of catalyst:polyme ⁇ zable compounds employed is from 10 ⁇ ' -: 1 to 10 " ' : 1 , more preferably from l ⁇ X l to 10" 5 : 1.
  • Suitable solvents for polymerization are inert liquids.
  • examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyciohexane.
  • cycloheptane methylcyclohexane, mcthylcycloheptane, and mixtures thereof; perfluo ⁇ nated hydrocarbons such as perfluo ⁇ nated C4_ J O alkanes, and the like and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, xylene, ethylbenzene and the like.
  • Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, butadiene, 1 - butene, cyclopentene, 1 -hexene, 1 -heptene, 4-v ⁇ nylcyclohexene, vinylcyclohexane, 3- methyl- 1 -pentene, 4-methyl-l-pentene, 1 ,4-hexad ⁇ ene, 1 -octene, 1 -decene, styrene, divinylbenzene, allylbenzene, vinyltoluene (including all isomers alone or in admixture), and the like. Mixtures of the foregoing are also suitable.
  • the catalyst systems may be utilized in combination with at least one additional homogeneous or heterogeneous polymerization catalyst in separate reactors connected in series or in parallel to prepare polymer blends having desirable properties.
  • An example of such a process is disclosed in WO 94/00500, equivalent to U S Serial Number 07/904,770, as well as U.S Serial Number 08/10958. filed January 29. 1993. the teachings oi which are hereby incorporated by reference herein
  • melt flow rates from 0 001 to 10 0 dg/ in are readily attained in a high temperature process
  • the catalyst systems of the present invention are particularly advantageous for the production of ethylene homopolymers and ethylene/ ⁇ -olefin copolymers having high levels of long chain branching
  • the use of the catalyst systems of the present invention in continuous polymerization processes, especially continuous, solution polymerization processes, allows for elevated reactor temperatures which favor the formation of vinyl terminated polymer chains that may be incorporated into a growing polymer, thereby giving a long chain branch
  • the use of the present catalysts system advantageously allows for the economical production of ethylene/ ⁇ -olefin copolymers having processabi ty similar to high pressure, free radical produced low density polyethylene
  • a preferred process is a high temperature solution polymerization process for the polymerization of oletins comprising contacting one or more C2-20 ot-olefins under polymerization conditions with a catalyst system of this invention at a temperature from about 100°C to about 250°C More preferred as a temperature range for this process is a temperature from about 120°C to about 200°
  • the present catalyst systems may be advantageously employed to prepare olefin polymers having improved processing properties by polymerizing ethylene alone or ethylene/ ⁇ -olefin mixtures with low levels of a "H" branch inducing diene, such as norbornadiene, 1 ,7-octad ⁇ ene, or 1 ,9-decad ⁇ ene
  • a "H" branch inducing diene such as norbornadiene, 1 ,7-octad ⁇ ene, or 1 ,9-decad ⁇ ene
  • a "H” branch inducing diene such as norbornadiene, 1 ,7-octad ⁇ ene, or 1 ,9-decad ⁇ ene
  • a "H” branch inducing diene such as norbornadiene, 1 ,7-octad ⁇ ene, or 1 ,9-decad ⁇ ene
  • such polymers are produced in a solution piocess. most preferably a continuous solution process Alternatively such polymers may be produced in a gas phase process or a slurry process
  • the present catalyst system is particularly useful in the preparation of EP and EPDM copolymers in high yield and productivity
  • the process employed may be either a solution or slurry process both of which are previously known in the art Kaminsky. J Poly Sci . Vol 23, pp 2151 -64 ( 1985) repo ⁇ ed the use of a soluble b ⁇ s(cyclopentad ⁇ enyl) zirconium dimethyl-alumoxane catalyst system for solution polymerization of EP and EPDM elastomers
  • U S 5,229,478 disclosed a slurry polymerization process utilizing similar b ⁇ s(cyclopentad ⁇ enyl) zirconium based catalyst systems
  • an olefin polymerization catalyst to a diene, especially the high concentrations of diene monomer required to produce the requisite level of diene incorporation in the final EPDM product, often reduces the rate or activity at which the catalyst will cause polymerization of ethylene and propylene monomers to proceed
  • lower throughputs and longer reaction times have been required, compared to the production of an ethylene-propylene copolymer elastomer or other ⁇ - olefin copolymer elastomer
  • the present catalyst system advantageously allows for increased diene reactivity thereby preparing EPDM polymers in high yield and productivity Additionally, the catalyst system of the present invention achieves the economical production of EPDM polymers with diene contents of up to 20 weight percent or higher, which polymers possess highly desirable fast cure rates
  • the nonconjugated diene monomer can be a straight chain, branched chain or cyclic hydrocarbon diene having from about 6 to about 15 carbon atoms.
  • suitable nonconjugated dienes are straight chain acyclic dienes such as 1 ,4-hexad ⁇ ene and 1 ,6-octad ⁇ ene, branched chain acyclic dienes such as 5-methyl-l ,4-hexad ⁇ ene, 3,7-d ⁇ methyl- l ,6-octad ⁇ ene, 3,7-d ⁇ methyl- l ,7-octad ⁇ ene and mixed isomers ol dihydromy ⁇ cene and dihydrooc ene, single ring alicyclic dienes such as 1 ,3-cyclopentad ⁇ ene, 1 ,4-cyclohexad ⁇ ene, 1 ,5-cyclooctad ⁇ ene and 1 ,5-cyclodode
  • 5-d ⁇ ene, alkenyl, alkylidene, cycloalkenyl and cycloalky dene norbornenes such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5- ⁇ sopropyl ⁇ dene-2- norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cycIohexyhdene-2-norbornene, 5- v ⁇ nyl-2-norbornene and norbornadiene
  • the particularly preferred dienes aie 1 ,4-hexad ⁇ ene (HD), 5-ethyl ⁇ dene-2-norbornene (ENB), 5-v ⁇ nyl ⁇ dene-2- noibornene (VNB), 5-methylene-2-norbornene (MNB ). and dicyclopentadiene (DCPD)
  • the especially preferred dienes are 5-ethyhdene-2-norbornene (ENB) and 1 ,4-hexad ⁇ ene (HD)
  • the preferred EPDM elastomers may contain about 20 up to about 90 weight percent ethylene, more preferably about 30 to 85 weight percent ethylene, most preferably about 35 to about 80 weight percent ethylene
  • alpha-olefins suitable for use in the preparation of elastomers with ethylene and dienes are preferably C3.
  • alpha-olefins Illustrative non-limiting examples of such alpha-olefins are propylene, 1 -butene 1 -pentene, 1 -hexene, 4- methyl- 1 -pentene, 1 -heptene, 1-octene, 1 -decene, and 1 -dodecene
  • the alpha-olefin is generally incorporated into the EPDM polymer at about 10 to about 80 weight percent, more preferably at about 20 to about 65 weight percent
  • the nonconjugated dienes are generally incorporated into the EPDM at about 0 5 to about 20 weight percent, more, preferably at about 1 to about 15 weight percent, and most preferably at 3 to about 12 weight percent If desired, more than one diene may be incorporated simultaneously, for example HD and ENB, with total diene incorporation within the limits specified
  • the catalyst system of this invention may comprise an aluminum organometalhc component which comprises an alumoxane, an aluminum alkyl or a combination thereof
  • This component may be present in a nonactivating amount and function primarily as a scavenger, or it may interact with the cocatalyst component to enhance the activity of the catalyst component, or it may do both
  • the catalyst or cocatalyst of the catalyst system can be covalently or lonically attached to the support material of the support component, which comprises a support material which is a polymer, an inorganic oxide, a metal halide, or a mixture thereof
  • Preferred supports for use in the present invention include highly porous silicas aluminas, aluminosilicates, and mixtures thereof
  • the most preferred support material is silica
  • the support material may be in granular, agglomerated, pelletized, or any other physical form. Suitable materials include, but are not limited to, silicas available from Grace Davison (division of W.R. Grace & Co ) under the designations SD 3216 30, Davison Syloid 245, Davison 948 and Davison 952, and from Crossfield under the designation ES70, and from Degussa AG under the designation Aerosil 812, and aluminas available from Akzo Chemicals Inc. under the designation Ketzen Grade B
  • Supports suitable for the present invention preferably have a surface area as determined by nitrogen porosimetry using the B E T. method from 10 to about 1000 n g, and preferably from about 100 to 600 ⁇ g.
  • the pore volume of the support, as determined by nitrogen adsorption, advantageously is between 0 1 and 3 cm ⁇ /g, preferably from about 0 2 to 2 c ⁇ X/g
  • the average particle size depends upon the process employed, but typically is from 0 5 to 500 ⁇ m, preferably from 1 to 100 ⁇ m.
  • Both silica and alumina are known to inherently possess small quantities of hydroxyl functionality.
  • these materials are preferably subjected to a heat treatment and/or chemical treatment to reduce the hydroxyl content thereof
  • Typical heat treatments are carried out at a temperature from 30°C to 1000°C (preferably 250°C to 800°C for 5 hours or greater) for a duration of 10 minutes to 50 hours in an inert atmosphere or under reduced pressure.
  • Typical chemical treatments include contacting with Lewis acid alkylating agents such as t ⁇ hydrocarbyl aluminum compounds, t ⁇ hydrocarbylchlorosilane compounds, t ⁇ hydrocarbylalkoxysilane compounds or similar agents. Residual hydroxyl groups are then removed via chemical treatment
  • Suitable functionalizing agents are compounds that react with surface hydroxyl groups of the support or react with the silicon or aluminum of the matrix. Examples of suitable functionalizing agents include phenylsilane, hexamethyldisilazane diphenylsilane, methylphenylsilane. dimethylsilane, diethylsilane, dichlorosilane, and dichlorodimethylsilane. Techniques for forming such functionahzed silica or alumina compounds were previously disclosed in U S Patents 3,687,920 and 3.879,368, the teachings of which arc herein incorporated by reference
  • the support may also be treated with an aluminum component selected from an alumoxane or an aluminum compound of the formula AIR ' x R- y , wherein R ' independently each occurrence is hydride or R, R- is hydride, R or OR, x' is 2 or 3, y' is 0 or 1 and the sum of x' and y' is 3
  • suitable R ' and R ⁇ groups include methyl, methoxy, ethyl, ethoxy, propyl (all isomers), propoxy (all isomers), butyl (all isomers), butoxy (all isomers), phenyl, phenoxy, benzyl, and benzyloxy
  • the aluminum component is selected from the group consisting of aluminoxanes and t ⁇ (C i .4 hydrocarbyOaluminum compounds Most preferred aluminum components are aluminoxanes. t ⁇ methylaluminum, t ⁇ ethylaluminum, t ⁇
  • Alumoxanes are oligomeric or polymeric aluminum oxy compounds containing chains of alternating aluminum and oxygen atoms, whereby the aluminum carries a substituent, preferably an alkyl group
  • the structure of alumoxane is believed to be represented by the following general formulae (-Al(R)-O) m ' , for a cyclic alumoxane, and R2Al-O(-Al(R)-O) rn '-AlR2, for a linear compound, wherein R is as previously defined, and m' is an integer ranging from I to about 50, preferably at least about 4
  • Alumoxanes are typically the reaction products of water and an aluminum alkyl, which in addition to an alkyl group may contain halide or alkoxide groups.
  • alumoxanes are methylalumoxane and methylalumoxane modified with minor amounts of C2-4 alkyl groups, especially isobutyl Alumoxanes generally contain minor to substantial amounts of starting aluminum alkyl compound
  • the treatment of the support material in order to also include optional alumoxane or t ⁇ alkylaluminum loadings involves contacting the same before, after or simultaneously with addition of the complex or activated catalyst hereunder with the alumoxane or trialkyialummum compound, especially t ⁇ ethylaluminum or tmsobutylaluminum.
  • the mixture can also be heated under an men atmosphere for a period and at a temperature sufficient to fix the alumoxane, trialkyialummum compound, complex or catalyst system to the support.
  • the treated support component containing alumoxane or the trialkyialummum compound may be subjected to one or more wash steps to remove alumoxane or trialkyialummum not fixed to the support.
  • the alumoxane may be generated in situ by contacting an unhydrolyzed silica or alumina or a moistened silica or alumina with a t ⁇ alkyl aluminum compound optionally in the presence of an inert diluent.
  • an unhydrolyzed silica or alumina or a moistened silica or alumina with a t ⁇ alkyl aluminum compound optionally in the presence of an inert diluent.
  • Suitable aliphatic hydrocarbon diluents include pentane, isopentane, hexane, heptane, octane, isooctane, nonane. isononane, decane, cyciohexane, methylcyclohexane and combinations of two or more of such diluents
  • Suitable aromatic hydrocarbon diluents are benzene, toluene, xylene, and other alkyl or halogen substituted aromatic compounds.
  • the diluent is an aromatic hydrocarbon, especially toluene
  • the residual hydroxyl content thereof is desirably reduced to a level less than 1 0 meq of OH per gram of support by any of the previously disclosed techniques
  • the cocatalysts of the invention may also be used in combination with a t ⁇ (hydrocarbyl)alum ⁇ num compound having from 1 to 10 carbons in each hydrocarbyl group, an oiigome ⁇ c or polymeric alumoxane compound, a d ⁇ (hydrocarbyl)(hydrocarbyloxy)alum ⁇ num compound having from 1 to 10 carbons in each hydrocarbyl or hydrocarbyloxy group, or a mixture of the foregoing compounds, if desired
  • These aluminum compounds are usefully employed for their beneficial ability to scavenge impurities such as oxygen, water, and aldehydes from the polymerization mixture
  • Preferred aluminum compounds include C2-6 tnalkyl aluminum compounds, especially those wherein the alkyl groups are ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl, or isopentyl, and methylalum
  • Solution polymerization takes place under conditions in which the diluent acts as a solvent for the respective components of the reaction, particularly the EP or EPDM polymer
  • Preferred solvents include mineral oils and the various hydrocarbons which are liquid at reaction temperatures
  • useful solvents include alkanes such as pentane, isopentane, hexane, heptane, octane and nonane, as well as mixtures of alkanes including kerosene and Isopar ETM, available from Exxon Chemicals Inc , cycloaikanes such as cyclopentane and cyciohexane, and aromatics such as benzene, toluene, xylenes, ethylbenzene and diethylbenzene
  • the reactions are performed in the presence of a dry, inert gas such as, for example, nitrogen Ethylene is added to the reaction vessel in an amount to maintain a differential pressure in excess of the combined vapor pressure of the ⁇ -olefin and diene monomers.
  • a dry, inert gas such as, for example, nitrogen Ethylene is added to the reaction vessel in an amount to maintain a differential pressure in excess of the combined vapor pressure of the ⁇ -olefin and diene monomers.
  • the ethylene content of the polymer is determined by the ratio of ethylene differential pressure to the total reactor pressure.
  • the polymerization process is carried out with a differential pressure of ethylene of from about 10 to about 1000 psi (70 to 7000 kPa), most preferably from about 40 to about 400 psi (30 to 300 kPa)
  • the polymerization is generally conducted at a temperature of from 25 to 200°C, preferably from 75 to 170°C, and most preferably from greater than 95 to 140°C.
  • the polymerization may be carried out as a batchwise or a continuous polymerization process.
  • a continuous process is preferred, in which event catalyst, ethylene, ⁇ -olefin. and optionally solvent and diene are continuously supplied to the reaction zone and polymer product continuously removed therefrom
  • continuous and continuous as used in this context are those processes in which there are intermittent additions of reactants and removal of products at small regular intervals, so that, over time, the overall process is continuous.
  • one means for carrying out such a polymerization process is as follows: In a stirred-tank reactor propylene monomer is introduced continuously together with solvent, diene monomer and ethylene monomer
  • the reactor contains a liquid phase composed substantially of ethylene, propylene and diene monomers together with any solvent or additional diluent If desired, a small amount of a "H"-branch inducing diene such as norbornadiene, 1 ,7-octad ⁇ ene or 1 ,9-decad ⁇ ene may also be added.
  • Catalyst and cocatalyst are continuously introduced in the reactor liquid phase.
  • the reactor temperature and pressure may be controlled by adjusting the solvent/monomer ratio, the catalyst addition rate, as well as by cooling or heating coils, jackets or both.
  • the polymerization rate is controlled by the rate of catalyst addition.
  • the ethylene content of the polymer product is determined by the ratio of ethylene to propylene in the reactor, which is controlled by manipulating the respective feed rates of these components to the reactor.
  • the polymer product molecular weight is controlled. optionally, by controlling other polymerization variables such as the temperature. monomer concentration, or by a stream of hydrogen introduced to the reactor, as is well known in the art.
  • the reactor effluent is contacted with a catalyst kill agent such as water
  • a catalyst kill agent such as water
  • the polymer solution is optionally heated, and the polymer product is recovered by flashing off gaseous ethylene and propylene as well as residual solvent or diluent at reduced pressure, and, if necessary, conducting further devoiatilization in equipment such as a devolati zing extruder
  • the mean residence time of the catalyst and polymer in the reactor generally is from about 5 minutes to 8 hours, and preferably from 10 minutes to 6 hours
  • the polymerization is conducted in a continuous solution polymerization system comprising two reactors connected in series or parallel
  • a relatively high molecular weight product (Mw from 300.000 to 600,000, more preferably 400.000 to 500,000) is formed while in the second reactor a product of a relatively low molecular weight (Mw 50,000 to 300,000) is formed
  • Mw 50,000 to 300,000 relatively low molecular weight
  • the final product is a blend of the two reactor effluents which are combined prior to devoiatilization to result in a uniform blend of the two polymer products
  • the reactors are connected in series, that is effluent from the first reactor is charged to the second reactor and fresh monomer, solvent and hydrogen i added to the second reactor Reactor conditions are adjusted such that the weight ratio of polymer produced in the first reactor to that produced in the second reactor is from 20 80 to 80.20
  • the temperature of the second reactor is controlled to produce the lower molecular weight product
  • the process of the present invention can be employed to advantage in the gas phase copolyme ⁇ zation of olefins.
  • Gas phase processes for the polymerization of olefins, especially the homopolymerization and copolyme ⁇ zation of ethylene and propylene, and the copolymerization of ethylene with higher ⁇ -olefins such as, for example, 1 -butene, 1 -hexene, 4-methyl- l -pentene are well known in the art.
  • Such processes are used commercially on a large scale for the manufacture of high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE) and polypropylene.
  • the gas phase process employed can be, for example, of the type which employs a mechanically stirred bed or a gas fluidized bed as the polymerization reaction zone.
  • Preferred is the process wherein the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported or suspended above a perforated plate, the tluidization grid, by a flow of fluidization gas.
  • the gas employed to fluidize the bed comprises the monomer or monomers to be polymerized, and also serves as a heat exchange medium to remove the heat of reaction from the bed.
  • the hot gases emerge from the top of the reactor, normally via a tranquilization zone, also known as a velocity reduction zone, having a wider diameter than the fluidized bed and wherein fine particles entrained in the gas stream have an opportunity to gravitate back into the bed. It can also be advantageous to use a cyclone to remove ultra-fine particles from the hot gas stream.
  • the gas is then normally recycled to the bed by means of a blower or compressor and one or more heat exchangers to strip the gas of the heat of polymerization.
  • a preferred method of cooling of the bed is to feed a volatile liquid to the bed to provide an evaporative cooling effect, often referred to as operation in the condensing mode.
  • the volatile liquid employed in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon having about 3 to about 8, preferably 4 to 6. carbon atoms.
  • the monomer or comonomer itself is a volatile liquid, or can be condensed to provide such a liquid, this can suitably be fed to the bed to provide an evaporative cooling effect.
  • olefin monomers which can be employed in this manner are olefins containing about three to about eight, preferably three to six carbon atoms.
  • the volatile liquid evaporates in the hot fluidized bed to form gas which mixes with the fluidizing gas. If the volatile liquid is a monomer or comonomer, it will undergo some polymerization in the bed.
  • the evaporated liquid then emerges from the reactor as part of the hot recycle gas, and enters the compression/heat exchange part of the recycle loop.
  • the recycle gas is cooled in the heat exchanger and, if the temperature to which the gas is cooled is below the dew point, liquid will precipitate from the gas. This liquid is desirably recycled continuously to the fluidized bed.
  • the polymerization reaction occurring in the gas fluidized bed is catalyzed by the continuous or semi-continuous addition of catalyst.
  • catalyst can be supported on an inorganic or organic support material as described above.
  • the catalyst can also be subjected to a prepolymerization step, for example, by polymerizing a small quantity of olefin monomer in a liquid inert diluent, to provide a catalyst composite comprising catalyst particles embedded in olefin polymer particles.
  • the polymer is produced directly in the fluidized bed by catalyzed copolymerization of the monomer and one or more comonomers on the fluidized particles of catalyst, supported catalyst or prepolymer within the bed.
  • Start-up of the polymerization reaction is achieved using a bed of preformed polymer particles, which are preferably similar to the target polyolefin, and conditioning the bed by drying with inert gas or nitrogen prior to introducing the catalyst, the monomers and any other gases which it is desired to have in the recycle gas stream, such as a diluent gas. hydrogen chain transfer agent, or an inert condensable gas when operating in gas phase condensing mode.
  • the produced polymer is discharged continuously or discontinuously from the fluidized bed as desired.
  • the gas phase processes suitable for the practice of this invention are preferably continuous processes which provide for the continuous supply of reactants to the reaction zone of the reactor and the removal of products from the reaction zone of the reactor, thereby providing a steady-state environment on the macro scale in the reaction zone of the reactor.
  • the fluidized bed of the gas phase process is operated at temperatures greater than 50°C, preferably from about 60°C to about 1 10°C, more preferably from about 70°C to about 1 10°C.
  • the molar ratio of comonomer to monomer used in the polymerization depends upon the desired density for the composition being produced and is about 0 5 or less. Desirably, when producing materials with a density range of from about 0.91 to about 0.93 the comonomer to monomer ratio is less than 0.2, preferably less than 0.05, even more preferably less than 0.02, and may even be less than 0 01 Typically, the ratio of hydrogen to monomer is less than about 0.5, preferably less than 0.2, more preferably less than 0.05, even more preferably iess than 0.02 and may even be less than 0.01.
  • the catalysts may be used to polymerize ethylemcally and/or acetylenically unsaturated monomers having from 2 to 100,000 carbon atoms either alone or in combination
  • Preferred monomers include the C2-20 ct-olefins especially ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1 -hexene, 3-methyl-l-pentene, 4-methyl- l -pentene, 1 -octene, 1 -decene, long chain macromolecular ⁇ -olefins, and mixtures thereof
  • the catalysts may also be utilized in combination with at least one additional homogeneous 01 heterogeneous polymerization catalyst in the same or in separate reactors connected in series or in parallel to prepare polymer blends having desirable properties
  • An example of such a process is disclosed in WO 94/00500, equivalent to U S Serial Number 07/904,770, as well as U S Serial Number 08/10958, filed January 29, 1993, the teachings or which are hereby incorporated by reference herein
  • the long chain branch is longer than the short chain branch that results from the incorporation of one or more ⁇ -olefin comonomers into the polymer backbone
  • the empirical effect of the presence of long chain branching in the copolymers of this invention is manifested as enhanced rheological properties which are indicated by higher flow activation energies, and greater L 1 /I 2 than expected from the other structural properties of the compositions
  • highly preferred polyolefin copolymer compositions of this invention have reverse molecular architecture, that is, there is a molecular weight maximum which occurs in that 50 percent by weight of the composition which has the highest weight percent comonomer content.
  • polyolefin copolymer compositions which also have long chain branches along the polymer backbone, especially when produced with a catalyst system of this invention having a single metallocene complex of this invention in a single reactor in a process for the polymerization of an ⁇ -olefin monomer with one or more olefin comonomers, more especially when the process is a continuous process
  • the comonomer content as a function of molecular weight can be measured by coupling a Fourier transform infrared spectrometer (FTIR) to a Waters 150°C Gel Permeation Chromatograph (GPC)
  • FTIR Fourier transform infrared spectrometer
  • GPC Waters 150°C Gel Permeation Chromatograph
  • the comonomer partitioning factor Cpf is calculated from GPC/FTIR data It characterizes the ratio of the average comonomer content of the higher molecular weight fractions to the average comonomer content of the lower molecular weight fractions Higher and lower molecular weight are defined as being above or below the median molecular weight respectively, that is, the molecular weight distribution is divided into two parts of equal weight.
  • c is the mole fraction comonomer content
  • w is the normalized weight fraction as determined by GPC/FTIR for the m FTIR data points below the median molecular weight Only those weight tractions, w, or w, which have associated mole fraction comonomer content values are used to calculate Cp [
  • Cpf desirably is equal to or greater than 1 10, more desirably is equal to ot greater than I 15 even more desirably is equal to or greater than 1 20, preferably is equal to or greater than 1 30 more preferably is equal to or greater than 1 40, even more preferably is equal to or greater than 1 50, and still more preferably is equal to or greater than 1 60
  • ATREF-DV has been described in U S Patent No 4,798.081 , which is hereby incorporated by reference, and in "Determination of Short-Chain Branching Distributions of Ethylene copolymers by Automated Analytical Temperature Rising Elution Fractionation" (Auto-ATREF), J of Appl Pol Sci Applied Polymer Symposium 45, 25-37 (1990)
  • ATREF-DV is a dual detector analytical system that is capable of fractionating semi-crystalline polymers like Linear Low Density Polyethylene (LLDPE) as a function of crystallization temperature while simultaneously estimating the molecular weight of the fractions
  • LLDPE Linear Low Density Polyethylene
  • ATREF-DV is analogous to Temperature Rising Elution Fractionation (TREF) analysis that have been published in the open literature over the past 15 years The primary difference is that this Analytical - TREF (ATREF) technique is done on a small scale and fractions are not actually isolated Instead, a typical liquid chromatographic (LC) mass
  • a commercially available viscometer especially adapted for LC analysis such as a ViskotekTM is coupled with the IR mass detector Together these two LC detectors can be used to calculate the intrinsic viscosity of the ATREF-DV eluant
  • the viscosity average molecular weight of a given fraction can then be estimated using appropriate Mark Houwink constants, the corresponding intrinsic viscosity, and suitable coefficients to estimate the fractions concentration (dl/g) as it passes through the detectors
  • a typical ATREF-DV report will provide the weight fraction polymer and viscosity average molecular weight as a function of elution temperature Mp is then calculated using the equation given
  • the molecular weight partitioning factor M p f is calculated from TREF/DV data It characterizes the ratio of the average molecular weight of the fractions with high comonomer content to the average molecular weight of the fractions with low comonomer content Higher and lower comonomer content are defined as being below or above the median elution temperature of the TREF concentration plot respectively, that is, the TREF data is divided into two parts of equal weight.
  • M p f is calculated from the following equation , where: M, is the viscosity average molecular weight and w, is
  • the normalized weight fraction as determined by ATREF-DV for the n data points in the fractions below the median elution temperature M is the viscosity average molecular weight and w, is the normalized weight fraction as determined by ATREF- DV for the m data points in the fractions above the median elution temperature Only those weight fractions, w, or w, which have associated viscosity average molecular weights greater than zero are used to calculate Mpf For a valid calculation, it is required that n and m are greater than or equal to 3
  • M p f desirably is equal lo or greater than 1 15, more desirably is equal to or greater than 1 30. even more desirably is equal to or greater than 1 40, preferably is equal to or greater than I 50, more preferably is equal to or greater than 1 60, even more preferably is equal to or greater than 1 70
  • Vanan XL-300 (FT 300 MHz, ' H, 75 MHz, ! 3 C) 1 H NMR and 3 C ( ! H ⁇ NMR spectra are referenced to the residual solvent peaks and are reported in ppm relative to tetramethylsilane. All J values are given in Hz. Mass spectra (El) were obtained on the AutoSpecQFDP. 1 -indanone, «-BuL ⁇ , Me2SiCh. NH2-f-Bu, NEt3 and MeMgl were purchased from Aldrich Chemical Co. All compounds were used as received.
  • N2.N2 Dimethyl- 1 -( 1 -(rerr-butylamino)- 1 , 1 -dimethylsilyl)- 1 H-2- ⁇ ndenam ⁇ ne, dilithium salt (3 40 g, 1 1.3 mmol) dissolved in 30 mL of THF was added within 2 minutes to a suspension of TiCl3(THF)3 (4.19 g, 1 1.3 mmol) in 60 mL of THF. After 1 hour of mixing, PbCh (2.04 g, 7 34 mmol) was added as a solid. The reaction mixture was stirred an additional 1.5 hours. The solvent was removed under reduced pressure.
  • a dark purple block-shaped crystal of dimensions 0.21 x 0 17 x 0 06 mm was immersed in oil, Paratone N, Exxon, and mounted on a thin glass fiber
  • the crystal was bathed in a cold nitrogen stream tor the duration of data collection (- 100 C)
  • Three sets of 20 frames each were collected covering three perpendicular sectors of space using the ⁇ scan method and with a ten second exposure time Integration of the frames followed by reflection indexing and least squares refinement produced a crystal orientation matrix and a monclinic lattice
  • the last run (# 5) is the rcmeasurement of the first 50 frames from run numbei 1 This is done to monitor crystal and diffractometer stability and to correct for any crystal decay
  • Diffractometer setup includes a 0 8 mm collimator providing an X-ray beam of 0 8 mm in diameter Generator power was set at 50 KV and 35 mA.
  • Program SMART' was usec j f or diffractometer control, fi me scans, indexing, orientation matrix calculations, least squares refinement of cell parameters, crystal faces measurements and the actual data collection Program ASTRO ' was used to set up data collection strategy
  • the structure was solved by direct methods in SHELXTL5 ⁇ from which the positions of all of the non-H atoms were obtained
  • the structure was refined, also in SHELXTL5, using full-matrix least-squares refinement
  • the non-H atoms were refined with anisotropic thermal parameters and all of the H atoms were located by a Difference Fourier map and refined without any constraints
  • 3639 observed reflections with I > 2s(I) were used to refine 313 parameters and the resulting R ] , WRT and S (goodness of fit) were 2 93 percent, 7 40 percent and
  • the structure was solved by direct methods in SHELXTL5 from which the positions of all of the non-H atoms were obtained
  • the structure was refined, also in SHELXTL5, using full-matrix least-squares refinement
  • the non-H atoms were refined with anisotropic thermal parameters and all of the H atoms were located by a Difference Fourier map and refined without any constraints.
  • 4838 observed reflections with I > 2 ⁇ (I) were used to refine 432 parameters and the resulting R ] , WR2 and S (goodness of fit) were 3.13 percent, 7. 17 percent and 1 .023, respectively.
  • linear absorption coefficient, atomic scattering factors and anomalous- dispersion corrections were calculated from values from the International Tables for X-ray Crystallography International Tables for X-ray Crystallography ( 1974). Vol. IV. p. 55. Birmingham: Kynoch Press. (Present distributor, D. Reidel, Dordrecht.).
  • Figure 1 shows the crystal structure of dichloro(N-( 1 , 1 -dimethylethyl)- 1 , 1 - dimethy 1- 1 -(( 1 ,2,3,3a,7a- ⁇ )-2-dimethyIamino- 1 H-inden- 1 -yl)silanaminato-(2-)-N-)- titanium.
  • R i A(IIF 0 I - IFcll) / AIF 0 I
  • wR 2 [A[w(Fo 2 - Fc 2 ) 2 ] / A[w(Fo 2 ) 2 ]] 1 /2
  • Rjnt. A IFo 2 - F 0 2 (mean)l 2 / A[F 0 2 ]
  • a translucent, red, platy crystal of ONSiTiCh i 7H25 having approximate dimensions of 0.4 x 0.2 x 0.06 mm was mounted using oil, (Paratone-N, Exxon) on a glass fiber.
  • Ail measurements were made on an Enraf-Nonius CAD4 diffractometer with graphite monochromated Mo-K ⁇ radiation.
  • the intensities of three representative reflection were measured after every 90 minutes of X-ray exposure time. No decay correction was applied.
  • the linear absorption coefficient, ⁇ . for Mo-K ⁇ radiation is 7.7 cm" ' .
  • An analytical absorption correction was applied which resulted in transmission factors ranging from 0.85 to 0.95.
  • the data were corrected for Lorentz and polarization effects.
  • the standard deviation of an observation of unit weight 0 was 1 47
  • the weighting scheme was based on counting statistics. Plots of ⁇ w(
  • Neutral atoms scattering factors were taken from Cromer and Waber (Cromcr. D T. & Waber, J T , "International Tables for X-Ray Crystallography", Vol, IV. The Kynoch Press, Birmingham, England. Table 2.2 A ( 1974)). Anomalous dispersion effects were included in Fcalc (Ibers, J.A. & Hamilton, W C , Acta Crystallogr , 17, 781 ( 1964)); the values for ⁇ f and ⁇ f" were those of Creagh and McAuley (Creagh, D.C. & McAuley, W. J ; "International Tables for Crystallography., Vol C , (A.J.C Wilson, ed.), Kluwer Academic Publishers.
  • Figure 2 shows the crystal structure of (N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 - a,7a- ⁇ )-2-ethoxy- 1 H-inden- 1 -yl)s ⁇ lanam ⁇ nato-(2-)-N-)-d ⁇ methyl-t ⁇ tan ⁇ um

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Abstract

This invention relates to heteroatom substituted cyclopentadienyl-containing ligands, metal complexes containing these ligands, catalyst systems prepared from catalyst components comprising these metal complexes. The metal complexes contain a heteroatom-Cp bond or a ring heteroatom-Cp bond in the 2-position of the Cp. In preferred metal complexes the ligand is a 2-heteroatom substituted indenyl group. The catalyst systems for olefin plymerization may be used at high temperatures, are highly active and produce high molecular weight polymer.

Description

2-HETEROATOM SUBSTITUTED CYCLOPENTADIENYL-CONTAINING METAL COMPLEXES AND OLEFIN POLYMERIZATION PROCESS
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of U S Provisional Application No 60/023,768 filed August 8, 1996
Field of the Invention
This invention relates to a class of metal complexes, the ligands used to prepare these metal complexes and to olefin polymerization catalysts derived therefrom that are particularly suitable for use in a polymerization process for preparing polymers by polymerization ol α-olefins and mixtures of α-olefins
Background
Constrained geometry metal complexes and methods tor their preparation are disclosed in U S Application Serial No 545,403, filed July 3, 1990 (EP-A-416 815), U S Application Serial No 547,718, filed July 3, 1990 (EP-A-468,651 ), U S Application Serial No 702,475, filed May 20, 1991 (EP-A-514,828), U S Application Serial No 876,268, filed May I , 1992, (EP-A-520,732) and U S Application Serial No 8,003, filed January 21, 1993 (WO 93/19104), as well as U S -A-5,055,438, U S - A-5 057,475, U S -A-5,096,867, U S -A-5,064,802, U S -A-5, 132,380, and WO- 95/00526 The teachings of all of the foregoing patents or the corresponding U S patent applications are hereby incorporated by reference
U S Patent No 's 5,350,817 and 5,304,614 disclose zirconium complexes with bπdged-metallocene ligands, wherein two indenyl groups are covalently linked together by a bridge containing carbon or silicon, which are useful for the polymerization of propylene
EP-A-577,581 discloses unsymmetrical bis-Cp metallocenes containing a fluorene ligand with heteroatom substituents E. Barsties; S. Schaible; M.-H. Prosenc; U. Rief; W. Roll, O. Weyland; B Dorerer; H.-H. Bπntzinger J Organometalhc Chem. 1996, 520, 63-68, and H. Plenio, D. Birth J Organometalhc Chem. 1996, 519, 269-272 disclose systems in which the cyclopentadienyl ring of the indenyl is substituted with a dimethylamino group in non- bridged and Si-bπdged bis-indenyl useful for the formation of isotactic polypropylene and polyethylene.
R. Leino; H. J. K. Luttikhedde; P. Lehmus; C.-E. Wilen; R. Sjohol ; A. Lehtonen; J. Seppala; J. H Nasman Macromolecules, 1997, 30, 3477-3488 disclose Co-bridged bis-indenyl metallocenes with oxygen in the 2-positιon of the indenyl group, and I. M. Lee; W. J Gauthier; J M. Ball; B Iyengar; S Collins
Organometallics, 1992, 11, 21 15-2122 discloses Co-bridged bis-indenyl metallocenes with oxygen in the 5,6-posιtιons of the indenyl group, while N. Piccolravazzi, P Pino, G. Consigho; A Sironi, M. Moret Organometallics, 1990, 9, 3098-3105 discloses non-bridged bis-indenyl metallocenes with oxygen in the 4- and 7-posιtιons of the indenyl group.
It has been thought that heteroatom-substitution, as opposed to carbon or hydrogen substitution, on any position of the indenyl system of a metallocene complex, when used in an olefin polymerization catalyst, renders the catalyst less active, that is, there is lower catalyst productivity for polymerizations with α-olefins, and the polymer produced has lower molecular weight with lower tacticity. It has been suggested that the diminished activity of this broad class of catalysts is due to interaction of the heteroatom lone pair electrons with the Lewis acid cocatalyst polymerization activator, resulting in a more electronically deactivated Cp ring which is also more steπcally hindered. SEE P. Foster; M. D Rausch, J. C. W Chien, J. Organometalhc Chem. 1996, 5/9, 269-272
Disclosure of random heteroatom substitution in mono-Cp metallocenes is found in EP-A-416,815, WO 95/07942, WO 96/13529, U.S. Patent No.'s 5,096.867 and 5,621 , 126 and related cases Up to now it has been thought that heteroatom substitution in metallocene complexes for use as olefin polymerization catalysts would have disadvantages due to unwanted interactions of the lone pair electrons of the heteroatom either with the transition metal atom of the same or a different metallocene molecule, or with other components of the catalyst system.
Numerous improvements in various metallocene complexes used as olefin polymerization catalysts have been made However, problems still remain with catalyst efficiency and deactivation of the catalyst under high temperature polymerization conditions It would be advantageous to be able to produce polyolefins with higher molecular weights It would also be advantageous to be able to improve other physical characteristics of the polymers produced by altering the substitution around the cyclopentadienyl group of the metallocene complexes used in olefin polymerization catalyst systems A new class of of the metallocene complexes for use in olefin polymerization catalyst systems may provide alternative solutions to the aforementioned problems which have advantages over other solutions
Summary of the Invention
According to the present invention there are provided metal complexes corresponding to the formula
Figure imgf000005_0001
where M is a metal from one of Groups 3 to 13 of the Periodic Table of the
Elements, the lanthanides or actinides, which is in the +2, +3 or +4 formal oxidation state and which is π-bonded to one cyclopentadienyl group (Cp) which is a cyclic, delocahzed, π-bound ligand group having 5 substituents: (RA),-T where j is zero, I or 2, RB; Rc , RD and 2, where RA, RB, R and RD are R groups, and where T is a heteroatom which is covalently bonded to the Cp ring, and to RA when j is 1 or 2, and when j is 0, T is F, Cl, Br, or I, when j is 1 , T is O or S, or N or P and RA has a double bond to T; when j is 2, T is N or P; and where
R independently each occurrence is hydrogen, or, is a group having from 1 to 80 nonhydrogen atoms which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl. hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilylhydrocarbyl, hydrocarbylamino, dι(hydrocarbyl)amιno, hydrocarbyloxy, each RA optionally being substituted with one or more groups which independently each occurrence is hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, dι(hydrocarbylsιlyl)amιno, hydrocarbylamino, dι(hydrocarbyl)amιno, dι(hydrocarbyl)phosphιno, hydrocarbylsulfido, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having from 1 to 20 nonhydrogen atoms, or a noninterfeπng group having from 1 to 20 nonhydrogen atoms, and each of RB, R and P IS hydrogen, or is a group having from 1 to 80 nonhydrogen atoms which is hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl, hydrocarbylsilylhydrocarbyl, each RB, RC or RD optionally being substituted with one or more groups which independently each occurrence is hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, dι(hydrocarbylsιlyl)amιno, hydrocarbylamino, dι(hydrocarbyl)amιno, dι(hydrocarbyl)phosphιno, hydrocarbylsulfido, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy- substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having from 1 to 20 nonhydrogen atoms, or a noninterfeπng group having from 1 to 20 nonhydrogen atoms; or, optionally, two or more of RA, RB, R and R are covalently linked with each other to form one or more fused rings or πng systems having from 1 to 80 nonhydrogen atoms for each R group, the one or more fused rings or ring systems being unsubstituted or substituted with one or more groups which independently each occurrence are hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, dι(hydrocarbylsιlyl)amιno, hydrocarbylamino, dι(hydrocarbyl)amιno, dι(hydrocarbyl)phosphιno, hydrocarbylsulfido, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy- substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having from 1 to 20 nonhydrogen atoms, or a noninterfeπng group having from 1 to 20 nonhydrogen atoms,
Z is a divalent moiety bound to both Cp and M via σ-bonds, where Z comprises boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprises nitrogen, phosphorus, sulfur or oxygen,
X is an anionic or dianionic ligand group having up to 60 atoms exclusive of the class of ligands that are cyclic, delocalized, π-bound ligand groups,
X' independently each occurrence is a neutral Lewis base ligating compound having up to 20 atoms,
p is zero, 1 or 2, and is two less than the formal oxidation state of M, when X is an anionic ligand, when X is a dianionic ligand group, p is 1 , and
q is zero, 1 or 2
The above complexes may exist as isolated crystals optionally in pure form or as a mixture with other complexes, in the form of a solvated adduct, optionally in a solvent, especially an organic liquid, as well as in the form of a dimer or chelated derivative thereof, wherein the chelating agent is an organic material, preferably a neutral Lewis base, especially a tπhydrocarbylamine, tπhydrocarbylphosphine, or halogenated derivative thereof
Also, according to the present invention, there is provided a catalyst system for olefin polymerization prepared from catalyst system components comprising (A) a catalyst component comprising a metal complex of one of the aforementioned complexes, and
(B) a cocatalyst component comprising an activating cocatalyst wherein the molar ratio of (A) to (B) is from 1 10,000 to 100 1 , or activation of (A) by use of an activating technique
Another embodiment of this invention is a catalyst system for olefin polymerization prepared from catalyst system components comprising
(A) a catalyst component comprising a metal complex of one of the aforementioned metal complexes, and
(B) a cocatalyst component comprising an activating cocatalyst wherein the molar ratio of (A) to (B) is from I 10,000 to 100 1
wherein the metal complex is in the form of a radical cation
Further according to the present invention there is provided a process for the polymerization of olefins comprising contacting one or more C2-20 c -olefins under polymerization conditions with one of the aforementioned catalyst systems
A preferred process of this invention is a high temperature solution polymerization process for the polymerization of olefins comprising contacting one or more C2-20 α-olefins under polymerization conditions with one of the aforementioned catalyst systems at a temperature from about 100°C to about 250°C
Within the scope of this invention are the polyolefin products produced by the aforementioned processes Preferred products have long chain branching and reverse molecular architecture
This invention also provides a cyclopentadienyl-containing ligand of one of the aforementioned metal complexes where the ligand is in the form of
(A) a free base with 2 protons capable of being deprotonated, (B) a dihthium salt,
(C) a magnesium salt or
(D) a mono or disilylated dianion
Within the scope of this aspect of the invention is the use of one of these ligands for synthesis to produce a metal complex of this invention, or for synthesis to produce a metal complex comprising a metal from one of Groups 3 to 13 of the Periodic Table of the Elements, the lanthanides or actinides, and from 1 to 4 of the ligands
The present catalysts and processes result in the highly efficient production of high molecular weight olefin polymers over a wide range of polymerization conditions, and especially at elevated temperatures They are especially useful tor the solution or bulk polymerization of ethylene/propylene (EP polymers), ethylene/octene (EO polymers), cthylene/styrene (ES polymers), propylene and ethylene/propylene/diene (EPDM polymers) wherein the diene is ethylidenenorbomene, 1 ,4-hexadιene or similar nonconjugated dienc The use of elevated temperatures dramatically increases the productivity of such processes due to the fact that increased polymer solubility at elevated temperatures allows the use of increased conversions (higher concentration of polymer product) without exceeding solution viscosity limitations of the polymerization equipment as well as reduced energy costs needed to devolatilize the reaction product
The catalysts of this invention may also be supported on a support material and used in olefin polymerization processes in a slurry or in the gas phase The catalyst may be prepolymeπzed with one or more olefin monomers in situ in a polymerization reactor or in a separate process with intermediate recovery of the prepolymeπzed catalyst prior to the primary polymerization process
Up to now it has been thought that heteroatom substitution directly on a cyclopentadienyl (Cp) group which is a cyclic, delocalized, π-bound ligand group of a metallocene complex would not have a beneficial effect upon the usefulness of the complex in an olefin polymerization catalyst system. However, it has now been found that the preferred metallocene complexes of this invention with heteroatom substitution directly on a single π-bonded Cp group have extraordinary properties as olefin catalysts, allowing the production of high molecular weight polymers with desirable characteristics at high catalyst activities Metallocene complexes with heteroatom substitution in the 2-posιtιon are highly preferred.
Brief description of the Figures
Figure 1 shows the crystal structure of dιchloro(N-( l , l-dιmethylethyl)-l, l- dimethyl- 1 -(( 1.2.3,3a,7a-η)-2-dιmethylamιno- 1 H-inden- 1 -y l)sιlanamιnato-(2-)-N-)- titanium.
Figure 2 shows the crystal structure of (N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1- (( 1 ,2,3.3a,7a-η)-2-ethoxy- 1 H-inden- 1 -yl)sιlanamιnato-(2-)-N-)-dιmethyl-tιtanιum.
Detailed Description
All reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc , 1989 Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups.
Olefins as used herein are C2-20 aliphatic or aromatic compounds containing vinylic unsaturation, as well as cyclic compounds such as cyclobutene, cyclopentene, and norbornene, including norbornene substituted in the 5- and 6- positions with C l-20 hydrocarbyl groups Also included are mixtures of such olefins as well as mixtures of such olefins with C4.40 diolefin compounds Examples of the latter compounds include ethy dene norbornene, 1 ,4-hexadιene, norbornadiene, and the like. The catalysts and processes herein are especially suited for use in preparation of ethylene/1 -butene, ethylene/1 -hexene, ethylene/styrene, ethylene/propylene, ethylene/1 -pentene, ethylene/4-methyl-l-pentene and ethylene/1-octene copolymers as well as terpolymers of ethylene, propylene and a nonconjugated diene, such as, for example, EPDM terpolymers
Preferred X' groups are carbon monoxide, phosphines, especially tπmethylphosphine, tπethylphosphine, tπphenylphosphine and bιs(l ,2- dιmethylphosphιno)ethane, P(OR')3, wherein R1 is hydrocarbyl, silyl or a combination thereof, ethers, especially tetrahydrofuran, amines, especially pyπdine, bipyπdine, tetramethylethylenediamine (TMEDA), and triethylamine, olefins, and conjugated dienes having from 4 to 40 carbon atoms Complexes including the latter X' groups include those wherein the metal is in the +2 formal oxidation state
Preferred coordination complexes according to the present invention are complexes corresponding to the formula
Figure imgf000011_0001
where R^, R^\ R * and R^ are R groups, each of which independently is hydrogen, or is a group having from 1 to 80 nonhydrogen atoms which is hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl, hydrocarbylsilylhydrocarbyl, each of R^, R^, R^ and R^ optionally being substituted with one or more groups which independently each occurrence is hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, dι(hydrocarbylsιlyl)amιno, hydrocarbylamino, dι(hydrocarbyl)amιno, dι(hydrocarbyl)phosphιno, hydrocarbylsulfido, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy- substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having from 1 to 20 nonhydrogen atoms, or a noninterfeπng group having from 1 to 20 nonhydrogen atoms, or, optionally, two or more of R^ , R^. R^, R^, RA and RB are covalently linked with each other to form one or more fused rings or ring systems having from 1 to 80 nonhydrogen atoms for each R group, the one or more fused rings or ring systems being unsubstituted or substituted with one or more groups which are hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino. dι(hydrocarbylsιlyl)amιno, hydrocarbylamino, dι(hydrocarbyl)amιno, dι(hydrocarbyl)phosphιno, hydrocarbylsulfido, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having from 1 to 20 nonhydrogen atoms, or a noninterfeπng group having from 1 to 20 nonhydrogen atoms
Preferred R^ groups are those wherein RA IS hydrocarbyl, hydrocarbylsilyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl and T is O or N, more preferred are those wherein RA u, hydrocarbyl or hydrocarbylsilyl and T is O or N, and still more preferred are wherein RA IS hydrocarbyl or hydrocarbylsilyl and T is O
Preferred heteroatom-containing substituents at the 2-posιtιon of the Cp are those wherein the (RA),-T group dimethylamino, diethylamino, methylethylamino, methylphenylammo, dipropylamino, dibutylammo, pipeπdinyl, morpholinyl, pyrro dinyl, hexahydro-l H-azepin- l-yl, hexahydro-l(2H)-azocιnyl, octahydro- 1 H- azonιn- 1-yl, octahydro- l(2H)-azecιnyl, methoxy, ethoxy, propoxy, methylethyloxy, 1 , 1-dιmethyethyloxy, tπmethylsiloxy or l , l-dιmethylethyl(dιmethylsιlyl)oxy
More preferred are those wherein the (RA).-T group is methoxy, ethoxy, propoxy, methylethyloxy, 1 , 1-dιmethyethyloxy, tπmethylsiloxy, 1 , 1 - dιmethylethyl(dιmethylsιlyl)oxy
In another aspect of this invention either the ligand or metal complex has one or more fused rings or ring systems in addition to the Cp or indenyl wherein the one or more fused rings or ring systems contain one or more ring heteroatoms which are N, O. S, or P Preferred ring heteroatoms are N or O, with N being more highly preferred.
Other highly preferred complexes correspond to the formula
Figure imgf000013_0001
where the symbols are as previously defined, or, more preferred, correspond to the formula
Figure imgf000013_0002
where the symbols are as previously defined
Highly preferred are the metal complexes and the heteroatom-containing ligands thereof where -Z- is -Z*-Y-, with Z* bonded to Cp and Y bonded to M, and
Y is -O-, -S-, -NR*-, -PR*-,
Z* is SιR*2, CR*2, SιR* SιR*2- CR*2CR*2< CR*=CR*, CR*oSιR*2> CR*2SιR*2CR*2, SιR*2CR*2SιR*2. CR*2CR* SιR*2, CR* CR*2CR*2> or GeR*2, and
R* independently each occurrence is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R* having up to 20 nonhydrogen atoms, and optionally, two R* groups from Z (when R* is not hydrogen), or an R* group from Z and an R* group from Y form a ring system,
where p is 2, q is zero, M is in the +4 formal oxidation state, and X is independently each occurrence methyl, benzyl, tπmethylsilylmethyl, allyl, pyrollyl or two X groups together are 1 ,4-butane-dιyl, 2-butene- 1 ,4-dιyl, 2,3-dιmethyl-2-butene- 1 ,4-dιyl, 2-methyl-2-butene-l ,4-dιyl, or xylyldiyl
Also highly preferred are the metal complexes and the heteroatom-containing ligands thereof where -Z- is -Z*-Y-, with Z* bonded to Cp and Y bonded to M, and
Y is -O-, -S-, -NR*-, -PR*-,
Z* is SιR*2- CR ' 2, SιR+2SιR*2< CR*2CR*2, CR*=CR*, CR*2SιR*2,
CR*2SιR*2CR*2- SιR*2CR*2SιR*2- CR*2CR*2SιR*2, CR*oCR*2CR*2. or GeR*2, and
R* independently each occurrence is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R* having up to 20 nonhydrogen atoms, and optionally, two R* groups from Z (when R* is not hydrogen), or an R* group from Z and an Rx group from Y form a ring system,
where p is 1 , q is zero, M is in the +3 formal oxidation state, and X is 2-(N,N- dιmethyl)amιnobenzyl, 2-(N,N-dιmethylamιnomethyl)phenyl, allyl, methallyl, tπmethylsilylallyl
Also highly preferred are the metal complexes and the heteroatom-containing ligands thereof where -Z- is -Z*-Y-, with Z* bonded to Cp and Y bonded to M. and
Y is -O-, -S-, -NR*-, -PR*-, Z * is SιR 2> CR*2, SιR*2SιR*2- CR*2CR*2, CR*=CR*, CR*2SιR*2- CR*2SιR*2 R*2' SιR*2CR*2SlR*2- CR*2CR*2SιR*2- CR*2CR χCR*2. or GeR*2- and
R* independently each occurrence is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R* having up to 20 nonhydrogen atoms, and optionally, two R* groups from Z (when R* is not hydrogen), or an R* group from Z and an R* group from Y form a ring system;
when p is 0, q is 1 , M is in the +2 formal oxidation state, and X' is 1.4- diphenyl- 1 ,3-butadιene, 1 ,3-pentadιene or 2,4-hexadιene
A variety of metals can be used in the preparation of the metal complexes of this invention, desirably a metal from one of Groups 3 to 13 of the Periodic Table of the Elements, the lanthanides or actinides, which is in the +2, +3 or +4 formal oxidation state, more desirably a metal from one of Groups 3 to 13 Metal complexes of this invention having somewhat different characteristics are those where M is a metal from one of Groups 3-6, one of Groups 7-9 or one of Groups 10-12. Preferred are those where M is a metal from Group 4, desirably Ti, Zr or Hf, with Ti and Zr being more preferred. Ti is the most highly preferred metal, especially for use in complexes which contain only one Cp-contaming ligand which is the heteratom- containing ligand of this invention, while Zr is highly preferred for use in complexes which contain two Cp-containmg ligands, at least one of which is a heteratom- containing ligand.
In one embodiment it is preferred that Ti is in the +4 formal oxidation state, while, alternatively it is preferred that Ti is in the +3 formal oxidation state, and more preferred is that Ti is in the +2 formal oxidation state
In another embodiment it is preferred that Zr is in the +4 formal oxidation state, or, alternatively, in the +2 formal oxidation state In another aspect of this invention it is preferred that Y is -NR \ with the more preferred -NR* being those where R* is a group having a primary or secondary carbon atom bonded to N Highly preferred are those where R* is cyclohexyl oi isopropyl
Illustrative derivatives of metals that may be employed in the practice of the present invention include
2-N-rheteroatom]t-Butylamιdo-ιndenyl complexes
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3 ,3a,7a-η)-2-( 1 -pyrro diny 1)- 1 H- inden- 1 -y l)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdinyl)- 1 H- inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(hexahydro- 1 H- azepin- 1 -yl)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-(l , 1 -Dimethylethyl)- 1 , 1 -dimethyl- ] -(( 1 ,2.3,3a,7a-η)-2-(hexahydro- 1 (2H)- azocinyl)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(octahydro- 1 H- azonin- 1 -yl)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(octahydro- 1 (2H)- azecinyl)- 1 H-inden- 1 -yl)sιlanamtnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιmethylamιno)- 1 H-inden- 1 -yl)(N-( 1 , 1 -dimethylethyl)- 1 , 1- dimethyl- 1 -(sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιethylamιno)- 1 H-inden- 1 -yl)(N-( 1 , 1 -dimethylethyl)- 1 , 1- dimethyl- 1 -(sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιpropylamιno)- 1 H-inden- 1 -yl)(N-( 1 , 1 -dimethylethyl)- 1 , 1 - dimethyl- 1 -(sιlanamιnato(2-)-N)dιmethyltιtanιum ( 1 ,2,3.3a.7a-η)-2-(Dιbutylamιno)- 1 H-inden- 1 -yl)(N-( 1 , 1 -dimethylethyl)- 1 , 1 - dimethy 1- 1 -(sιlanamιnato(2-)-N)dιmethyltιtanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(ethylmethylamιno)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethy Ititanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2.3,3a,7a-η)-2-
(methylphenylamιno)-l H-inden- l -yl)silanaminato(2-)-N)dimethyltitanium
(N-( 1.1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2- (methyl(phenylmethyl)amιno)-lH-ιnden-l-yl)silanammato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(( 1 , 1 - dιmethylethyl)methylamιno)-l H-inden- l-yl)silanaminato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(methyI( 1 - methylethyl)amιno)-l H-ιnden- l-yl)sιlanaminato(2-)-N)dimethy Ititanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2- (diphenylphosphino)- 1 H-inden- 1 -yl)silanamιnato(2-)-N)dimethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-
(dimethylphosphino)- 1 H-inden- 1 -y l)silanaminato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2- ( me thy Ipheny Iphosphino)- 1 H-inden- 1 -yl)silanaminato(2-)-N)dimethy Ititanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(dιethylphosphιno)- 1 H-inden- 1 -yl)sιianamιnato(2-)-N)dimethyltιtanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(bis( 1 - methylethy l)phosphιno)- 1 H-inden- 1 -yl)silanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1.1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-methoxy- 1 H-inden- l-yl)sιlanamιnato(2-)-N)dιmethyltιtanιum (N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-ethoxy- 1 H-inden- 1 - y])sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2.3 3a.7a-η)-2-propoxy- 1 H-tnden- l-yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-butoxy- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)dιmethy Ititanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1.2,3,3a.7a-η )-2-(( 1 , 1 - dimethy lethy l)oxy)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(tπmethylsιloxy )- l H-ιnden- l-yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-((( 1.1 - dιmethylethyl)dιmethylsιlyl)oxy)- 1 H-mden-l-yl)sιlanamιnato(2-)-N)dιmethy Ititanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -methylethoxy)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-phenoxy- 1 H-inden- l -yi)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(phenylthιo)- 1 H- mden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(methylthιo)- 1 H- inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
3-methyl-2-N-Fheteroatom1t-Butylamιdo-ιndenyl complexes
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-( 1 - pyrrolιdιnyl)-lH-ιnden- l -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum (N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-( 1 - piperidinyl)- 1 H-inden- 1 -yl)silanaminato(2-)-N)dimethyltitanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (hcxahydro- 1 H-azepin- 1 -yl)- 1 H-inden- 1 -y l)silanaminato(2-)-N)dimethyltitanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-
(hexahydro- 1 (2H)-azocinyl)- 1 H-inden- 1 -yl)silanaminato(2-)-N)dimethyltitanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (octahydro- 1 H-azonin- 1 -yl)dimethyltitanium
(N-(l , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (octahydro- l (2H)-azecinyl)-l H-inden- l-yl)siianaminato(2-)-N)dimethyltitanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (dimethylamino)- l H-inden- l-yl)silanaminato(2-)-N)dimethyltitanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (diethylamino)-l H-inden- l-yl)silanaminato(2-)-N)dimethy Ititanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-
(dipropylamino)- 1 H-inden- 1 -yI)silanaminato(2-)-N)dimethyltitanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3.3a,7a-η)-3-methyl-2- (dibuty lamino)- 1 H-inden- 1 -y l)silanaminato(2-)-N)dimethy Ititanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (ethylmethylamino)-l H-inden- l-yl)silanaminato(2-)-N)dimethy Ititanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (methylphenylamino)-l H-inden- l-yl)silanaminato(2-)-N)dimethyltitanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- ( ethy l(phenylmethyl)amino)- 1 H-inden- 1 -y l)silanaminato(2-)-N)dimethyltitanium (N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methy l-2-(( 1 , 1 - dimethy lethyOmethylammo)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2.3,3a,7a-η)-3-methy l-2-(methy 1( 1 - methylethyl)amιno)-lH-ιnden- l-yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-
(dιpheny]phosphιno)-lH-ιnden- l -y0sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a.7a-η)-3-methyl-2- (dimethylphosphino)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethy Ititanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (methylphenylphosphmo)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1.1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (diethyiphosphino)- 1 H-inden- 1 -y l)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-(bιs( 1 - methylethy phosphino)- 1 H-mden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-methoxy-
1 H-inden- 1 -y l)sιlanamιnato(2-)-N)dιmethyItιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-ethoxy- 1 H-mden- 1 -y l)sιlanammato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-propoxy- 1 H-inden- 1 -y l)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-butoxy- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methy l-2-(( 1 , 1 - dιmethylethyl)oxy)-lH-ιnden-] -yl)sιlanamιnato(2-)-N)dιmethyltιtanium (N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a.7a-η)-3-methyl-2- (tπmethylsιloxy)-lH-ιnden- l-yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-((( 1.1 - dιmethylethyl)dιmethylsιlyl)oxy)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3.3a,7a-η)-3-methyl-2-( 1 - methylethoxy)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyI-2-phenoxy- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (phenylthio)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3.3a,7a-η)-3-methyl-2- (methylthιo)- l H-ιnden-l-yl)sιianamιnato(2-)-N)dιmethyltιtanιum
2-N-heteroatomfamιdol-ιndenyl complexes
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the N-( 1 , 1 -dimethylethyl) group is replaced by N-cyclohexyl as demonstrated by the following compounds
(N-Cyclohexyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrohdinyl)- 1 H-inden- 1 - yI)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Cyclohexy 1- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdiny I)- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3, 3a,7a-η)-2-(Dιmethylamιno)-l H-ιnden- l-yl)(N-cyclohexy 1-1 , 1 -dimethyl- l -(sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιethylamιno)-l H-inden- 1 -yl)(N-cyclohexy 1- 1 , 1 -dimethyl- l -(sιianammato(2-)-N)dιmethyltιtanιum (N-Cyclohexyl-1.1 -dimethyl- 1 -((l,2,3,3a,7a-η)-3-methyl-2- (ethylmethylamιno)-lH-ιnden- l-yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Cyclohexyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (methylphenylamιno)-l H-mden- l-yl)sιlanammato(2-)-N)dιmethyltιtanιum
(N-Cyclohexyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-methoxy- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Cyclohexyl-l , l-dιmethyl- l -(( l,2,3,3a,7a-η)-2-(( l ,l -dιmethylethyl)oxy)-lH- mden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Cyclohexyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(tπmethylsιloxy)- lH-inden- l -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Cyclohexyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-(dιmethylamιno)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the N-( 1 , 1 -dimethylethyl) group is replaced by N-methyl as demonstrated by the following compounds
(N-methyl- 1 , 1 -dimethyl- 1-(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrohdinyl)- IH-inden- 1 - yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-methyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdiny 1)- 1 H-inden- 1 - yI)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a,7a-η)-2-(dιmethylamιno)- 1 H-inden- 1 -yl)(N-methyl- 1 , 1 -dimethyl- 1 -
(sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιethy lamino)- 1 H-inden- 1 -y l)(N-methyl- 1 , 1 -dimethyl- 1 - (sιlanamιnato(2-)-N)dιmethyltιtanιum (N-Methyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-(ethyimethylamιno)- lH-ιnden- l-yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Methyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-(methylpheny laminoV 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Methyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-methoxy- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)dιmethyItιtanιum
(N-Methyl- 1 , 1 -dιmethyl-1 -(( 1 ,2,3,3a,7a-η)-2-(( 1 , 1 -dimethylethy Doxy)- 1 H- mden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Methyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(tπmethy Isiloxy)- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Methyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methy l-2-(dιmethy lamino)- 1 H- mden- 1 -yI)sιlanamιnato(2-)-N)dιmethyltιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the N-( 1 , 1 -dimethylethyl) group is replaced by N-ethyl as demonstrated by the following compounds
(N-Ethyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3.3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Ethyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdiny I)- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιmethylamιno)- 1 H-inden- 1 -yl)(N-ethyl- 1 , 1 -dimethyl- 1 -
(sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιethylamιno)- 1 H-inden- 1 -yl)(N-ethyl- 1 , 1 -dimethyl- 1 - (sιlanamιnato(2-)-N)dιmethyltιtanιum (N-Ethyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-(ethylmethylamιno)- 1 H- mden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Ethyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-(methylphenylamιno)- l H-ιnden-l -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Ethyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-methoxy- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)dιmethy Ititanium
(N-Ethyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(( 1 , 1 -dimethy lethy l)oxy )- 1 H- mden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Ethyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(tπmethylsιloxy)- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)dιmethyltιtamum
(N-Ethyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-(dιmethylamιno)- 1 H- mden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
In the above names where 2-heteroatom-ιndenyl complexes arc named, a similar range of compounds are those where the N-( 1 ,1 -dimethylethyl) group is replaced by N-phenyl as demonstrated by the following compounds
( 1 , 1 -Dimethyl-N-phenyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidiny I)- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 , 1 -Dimethy l-N-phenyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdiny 1)- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιmethy lamino)- 1 H-mden- 1 -yl)( 1 , 1 -dimethy l-N-phenyl- 1 -
(sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιethylamιno)- 1 H-inden- 1 -yl)( 1 , 1 -dimethyl-N-phenyl- 1 - (sιlanamιnato(2-)-N)dιmethyltιtamum ( 1 , 1 -Dimethyl-N-phenyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-(ethylmethylamιno)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 , 1 -Dimethyl-N-phenyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-(methylphenylamιno)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethy Ititanium
( 1, 1 -Dimethyl-N-phenyl- 1 -(( 1 ,2,3,3a,7a-η)-2-methoxy- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)dιmethyltιtamum
( 1 , 1 -Dimethyl-N-phenyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(( 1 , 1 -dimethylethyOoxy)- 1 H- mden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 , 1 -Dimethy l-N-phenyl- 1-(( 1 ,2,3,3a,7a-η)-2-(tπmethylsιloxy)- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 , 1 -Dimethy l-N-phenyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-(dιmethylamιno)- 1H- mden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the N-( 1 , 1 -dimethylethyl) group is replaced by N-phenylmethyl as demonstrated by the following compounds
( 1 , 1 -Dιmethyl-N-(phenylmethyΙ)- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H- mden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 , 1 -Dιmethyl-N-(phenylmethyl)- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdiny 1)- 1 H- inden- 1 -y l)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιmethy lamino)- 1 H-mden- 1 -yl)( 1 , 1 -dimethy I-N-
(phenylmethyl)- 1 -(sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a.7a-η)-2-(Dιethylammo)- 1 H-inden- 1 -yl)( 1 , 1 -dimethyl-N- (phenylmethyl)- 1 -(sιlanamιnato(2-)-N)dιmethyltιtanιum ( 1 , 1 -Dιmethyl-N-(phenylmethyl)- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (ethy lmethylamino)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,1 -Dιmethyl-N-(phenylmethyl)- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- ( methy Ipheny lamino)- 1 H-inden- 1 -y l)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 , 1 -Dιmethyl-N-(phenylmethyl)- 1 -(( 1 ,2,3,3a,7a-η)-2-methoxy- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,1 -Dιmethyl-N-(phenylmethyl)- 1 -(( 1 ,2,3,3a,7a-η)-2-(( 1 , 1 - dιmethylethyl)oxy)-l H-ιnden- l -yl)sιlanamιnato(2-)-N dιmethyltιtanιum
( 1 , 1 -Dιmethyl-N-(phenylmethyl)- 1 -(( 1 ,2,3,3a,7a-η)-2-(tπmethylsιloxy )- 1 H- inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 , 1 -Dιmethyl-N-(phenylmethyl)-l -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (dimethy lamino)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
In the above names where 2-heteroatom-ιndenyl complexes arc named, a similar range of compounds are those where the N-( 1.1 -dimethylethyl) group is replaced by N-cyclododccyl as demonstrated by the following compounds
(N-Cyclododecyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H-inden- l -yπsιlanamιnato(2-)-N)dιmethy Ititanium
(N-Cyclododecyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdiny 1)- 1 H-inden- l-yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Cyclododecyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(dιmethylamιno)- 1 H- ιnden- l-yl)sιlanamιnato(2-)-N)dιmethy]tιtanιum
(N-Cyclododecyl- 1 , 1 -dimethyl- 1 -( 1 ,2,3,3a,7a-η)-2-(Dιethylamιno)- 1 H-inden- l -yl)-(sιlanamιnato(2-)-N)dιmethyItιtamum (N-Cyclododecyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3.3a,7a-η)-3-methyl-2- (ethylmethylamino)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Cyclododecyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (methylphenyiamιno)-lH-ιnden-l -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-cyclododecy 1- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-methoxy- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)dιmethy Ititanium
(N-cyclododecy 1- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(( 1 , 1 -dimethy lethy l)oxy )- l H-ιnden- l-yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-cyclododecy 1-1, 1 -dimethyl- 1-(( 1 ,2,3 ,3a,7a-η)-2-(tπmethylsιloxy)- lH-ιnden- l -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-cyclododecyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-(dιmethylamιno)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the N-( 1 , 1 -dimethylethyl) group is replaced by N-methylethyl as demonstrated by the following compounds
( 1 , 1 -Dιmethyl-N-(methylethyl)- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H-inden- l-yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 , 1 -Dιmethyl-N-(methylethyl)- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdmyl)- 1 H-inden- l -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a.7a-η)-2-(Dιmethylamιno)- 1 H-inden- 1 -y!)( 1 , 1 -dimethyl-N-
(methylethyl)- 1 -(sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιethylamιno)- 1 H-inden- 1 -yl)( 1 , 1 -dimethyl-N- (methylethyl)- 1 -(sιlanamιnato(2-)-N)dιmethyltιtanιum ( 1 , 1 -Dιmethyl-N-(methylethyl)- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (ethylmethylamino)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1, 1 -Dimethy l-N-(methy lethyl)- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (methylphenylamino)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 , 1 -Dιmethyl-N-(methylethyl)- 1 -(( 1 ,2,3,3a,7a-η)-2-methoxy- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(1 , 1 -Dιmethyl-N-(methylethyl)- 1 -(( 1 ,2,3,3a,7a-η)-2-(( 1 , 1 -dιmethylethyl)oxy)- lH-mden- l-yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( l , l-Dιmethyl-N-(methylethyl)-l-((l ,2,3,3a,7a-η)-2-(tπmethylsιloxy)-l H- inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 , 1 -Dιmethyl-N-(methy lethyl)- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (dimethylamino)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
2-N-fheteroatoml[amιdelTιX2-ιndenyl complexes
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the two methyls bound to the titanium are replaced by chlorides as demonstrated by the following compounds
Dιchloro(N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 - pyrrolidinyl)- l H-ιnden- l -yl)sιlanamιnato(2-)-N)tιtanιum
Dιchloro(N-cyclohexy 1- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdinyl)- 1 H- inden- 1 -yl)sιlanamιnato(2-)-N)tιtanιum
Dιchloro(N-methyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a.7a-η)-2-(dιmethylamιno)- 1 H- lnden- 1 -yl)sιlanamιnato(2-)-N)tιtanιum
Dιchloro(N-methyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(dιethylamιno)- 1 H- inden- 1 -yl)sιlanamιnato(2-)-N)tιtanιum Dιchloro(N-ethyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methy 1-2- (ethy lmethylamino)- 1 H-inden- 1 -yl)sιIanamιnato(2-)-N)tιtanιum
Dιchloro( 1 , 1 -Dimethyl-N-phenyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (methylphenylamιno)-l H-ιnden- l-yl)sιlanamιnato(2-)-N)tιtanιum
Dιchloro( 1 , 1 -Dιmethyl-N-(phenylmethyl)- 1 -(( 1 ,2,3,3a.7a-η)-3-methyl-2-
(methy Ipheny lamino)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)tιtanιum
Dιchloro(N-cyclododecyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (methylphenylamιno)-l H-ιnden- l-yl)sιlanamιnato(2-)-N)tιtanιum
Dιchloro(N-methyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(dιmethy lamino)- 1 H- inden- 1 -yl)sιlanamιnato(2-)-N)tιtanιum
Dιchloro(N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3.3a,7a-η)-2-methoxy- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)tιtanιum
Dιchloro(N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-((( 1 , 1 - dιmethylethyl)dιmethylsιlyl)oxy)-l H-inden- l -yl)sιlanamιnato(2-)-N)tιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the two methyls bound to the titanium are replaced by phenylmethyl as demonstrated by the following compounds
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H- mden- l-yl)sιlanamιnato(2-)-N)bιs(phenylmethyl)tιtanιum
(N-Cyclohexyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdinyl)- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)bιs(phenylmethyl)tιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιmethylamιno)- IH-inden- 1 -yl)(N-methyl- 1 , 1 -dimethyl- 1 - (sιlanamιnato(2-)-N)bιs(phenylmethyl)tιtamum ( 1 ,2,3,3a.7a-η)-2-(Dιethylamιno)- 1 H-inden- 1 -yl)(N-methyl- 1 , 1 -dimethyl- 1 - (sιlanamιnato(2-)-N)bιs(phenylmethyl)tιtanιum
(N-ethyl- 1 , 1 -Dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methy l-2-(ethylmethylamιno)- 1 H- mden- 1 -y!)sιlanamιnato(2-)-N)bιs(phenylmethyl)tιtanιum
( 1 , 1 -Dimethyl-N-phenyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-(methylphenylamιno)- lH-ιnden- l-yl)sιlanamιnato(2-)-N)bιs(phenylmethyl)tιtanιum
( l , l-Dιmethyl-N-(phenylmethyl)-l-((l,2.3,3a,7a-η)-3-methyl-2- (methylphenylamιno)-lH-ιnden-l -yl)sιlanamιnato(2-)-N)bιs(phenylmethyl)tιtanιum
(N-Cyclododecyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (methylphenylamιno)- l H-ιnden- l-yl)sιlanamιnato(2-)-N)bιs(phenylmethyl)tιtanιum
( 1 ,2,3,3a.7a-η)-2-(dιmethyiamιno)- 1 H-inden- 1 -yl)(N-methy I- 1 , 1 -dimethyl- 1 - (sιlanamιnato(2-)-N)bιs(phenylmethyl)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-methoxy- 1 H-inden- l-yl)sιlanamιnato(2-)-N)bιs(phenylmethyl)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1-(( 1 ,2,3,3a,7a-η)-2-((( 1 , 1 - dιmethylethyl)dιmethylsιlyl)oxy)- lH-ιnden- l -yl)sιlanamιnato(2-)- N)bιs(phenylmethyl)tιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the two methyls bound to the titanium are replaced by (tπmethylsιlyl)methyl as demonstrated by the following compounds
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H- ιnden- l -yl)sιlanamιnato(2-)-N)bιs((tπmethylsιlyl)methyl)tιtanιum
(N-Cyclohexyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdinyl)- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)bιs((tπmethylsιlyl)methyl)tιtanιum ( 1 ,2,3,3a,7a-η)-2-(Dιmethylamιno)- 1 H-inden- 1 -yl)(N-methy 1- 1 , 1 -dimethyl- 1 - (sιlanamιnato(2-)-N)bιs((tπmethylsιlyl)methyl)tιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιethy lamino)- 1 H-inden- 1 -y l)(N-methy 1- 1.1 -dimethyl- 1 - (sιlanamιnato(2-)-N)bιs((tπmethylsιlyl)methyl)tιtanιum
(N-Ethyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methy l-2-(ethylmethylamιno)- 1 H- ιnden- l -yl)sιlanamιnato(2-)-N)bιs((trimethylsilyl)methyl)tιtanιum
( 1 , 1 -Dimethyl-N-phenyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyI-2-(methylphenylamιno)- 1 H-inden- 1 -yl)silanamιnato(2-)-N)bιs((tπmethylsιlyl)methyl)tιtanιum
( 1 , 1 -Dιmethyl-N-(ρhenylmethyl)- 1 -(( 1 ,2,3,3a,7a-η)-3-methy 1-2- (methylphenylamino)- 1 H-inden- 1 -yl)sιlanamιnato(2-)- N)bιs((tπmethylsιlyl)methyl)tιtanιum
(N-Cyclododecyl- 1 , 1 -dimethyl- 1-(( 1 ,2,3,3a,7a-η)-3-methyl-2- (methylphenylamino)- 1 H-inden- 1 -yl)sιlanamιnato(2-)- N)bιs((tπmethylsιlyl)methyl)tιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιmethylamιno)- 1 H-inden- 1 -yl)(N-methyl- 1 , 1-dιmethyl- 1 -
(sιlanamιnato(2-)-N)bιs((tπmethylsιlyl)methyl)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-methoxy- 1 H-inden- l -yl)sιlanamιnato(2-)-N)bιs((tπmethylsιlyl)methyl)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-((( 1 , 1 - dimethylethy l)dιmethylsιlyl)oxy)- 1 H-inden- 1 -yl)sιlanamιnato(2-)- N)bιs((tπmethylsιlyl)methyl)tιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the two methyls bound to the titanium are replaced by 2,2-dιmethyIpropyl as demonstrated by the following compounds (N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a.7a-η)-2-( 1 -pyrrolidinyl)- 1 H- mden- 1 -yl)sιlanamιnato(2-)-N)bιs(2,2-dιmethylpropyl)tιtanιum
(N-Cyclohexyl- 1 , 1 -dimethy I- 1 -(( 1 ,2,3,3a,7a-η)-2- 1 -pipeπdinyl)- 1 H-inden- 1 - yl)sι!anamιnato(2-)-N)bιs(2,2-dιmethylpropyl)tιtamum
( 1 ,2,3,3a,7a-η)-2-(Dιmethylamιno)- 1 H-inden- 1 -yl)(N-methyl- 1 , 1 -dimethyl- 1 -
(sιlanamιnato(2-)-N)bιs(2,2-dιmethylpropyl)tιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιethy lamino)- 1 H-ιnden-1 -yl)(N-methyl- 1 , 1 -dimethyl- 1 - (sιlanamιnato(2-)-N)bιs(2,2-dιmethylpropyl)tιtanιum
(N-ethyl- 1 , 1 -Dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-meth l-2-(ethylmethy lamino)- 1 H- inden- 1 -yl)sιlanamιnato(2-)-N)bιs(2,2-dιmethylpropyl)tιtanιurn
( 1 , 1 -Dimethy l-N-phenyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-(methy Ipheny lamino)- lH-ιnden- l -yl)sιlanamιnato(2-)-N)bιs(2,2-dιmethylpropyl)tιtanιum
( 1 , 1 -Dimethy l-N-(phenylmethyl)- 1 -(( 1 ,2,3,3a,7a-η)-3-methy 1-2- (methylphenylamιno)-l H-ιnden- l -yI)sιlanamιnato(2-)-N)bιs(2,2- dιmethylpropyl)tιtanιum
(N-Cyclododecyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (methylphenylamino)- 1 H-inden- l-yl)sιlanamιnato(2-)-N)bιs(2,2- dιmethylpropyl)tιtanιum
(N-Methyl- 1 , 1-dιmethy 1- 1 -(( 1 ,2,3,3a,7a-η)-2-(dιmethylamιno)- 1 H-mden- 1 - yl)sιlanamιnato(2-)-N)bιs(2,2-dιmethy]propyl)tιtanιurn
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-methoxy- 1 H-inden- l -yl)sιlanamιnato(2-)-N)bιs(2,2-dιmethylpropyl)tιtanιum
(N-( 1.1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2.3,3a,7a-η)-2-((( 1 , 1 - dιmethylethyl)dιmethylsιlyl)oxy)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)bιs(2.2- dtmethylpropyl)tιtanιum In the above names where 2-heteroatom-indenyl complexes are named, a similar range of compounds are those where the two methyls bound to the titanium are replaced by a single 2-((dimethylamino)methyl)phenyl as demonstrated by the following compounds.
(2-((Dimethylamino)methyl)phenyl)(N-( 1 ,1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -
(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H-inden- 1 -yl)silanaminato(2-)-N)titanium
(N-Cyclohexyl- 1 , 1 -dimethyl(2-((dimethylamino)methyl)phenyl)- 1 - (( 1 ,2,3,3a,7a-η)-2-( 1 -piperidinyl)- 1 H-inden- 1 -yl)siIanaminato(2-)-N)titanium
(2-((Dimethylamino)methyl)phenyl)(N-methyl- 1 , 1 -dimethyl- 1-(( 1 ,2,3,3a,7a-η)- 2-(dimethylamino)- 1 H-inden- 1 -y!)silanaminato(2-)-N)titanium
(2-((Dimethy lamino)methy l)phenyl)(N-ethyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a.7a-η)- 3-methyl-2-(ethylmethylamino)-l H-inden- l-yl)silanaminato(2-)-N)titanium
(2-((Dimethylamino)methyl)phenyl)( 1 , 1 -dimethyl-N-phenyl- 1 -(( 1 ,2,3,3a,7a-η)- 3-methyl-2-(methylpheny lamino)- 1 H-inden- 1 -y!)silanaminato(2-)-N)titanium
(2-((Dimethylamino)methyl)phenyl)( 1 , 1 -dimethyl-N-(pheny lmethyl)- 1 -
(( 1 ,2,3,3a.7a-η)-3-methyi-2-(methylphenylamino)- 1 H-inden- 1 -yl)silanaminato(2-)- N)titanium
(N-Cyclododecyl- 1 , 1 -dimethy I(2-((dimethylamino)methyl)phenyl)- 1 - (( 1 ,2,3,3a,7a-η)-3-methyl-2-(methylphenylamino)- 1 H-inden- 1 -y l)silanaminato(2-)- N)titanium
(2-((Dimethylamino)methyI)phenyl)(N-methyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)- 2-(dimethylamino)- 1 H-inden- 1 -yl)silanaminato(2-)-N)titanium
(2-((Dimethylamino)methyl)phenyl)(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 - (( 1 ,2,3,3a,7a-η)-2-methoxy- 1 H-inden- 1 -yl)silanaminato(2-)-N)titanium (2-((Dιmethylamιno)methyl)pheny I)(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 - (( 1 ,2.3.3a,7a-η)-2-((( 1 , 1 -dimethy lethyl)dιmethylsιlyl)oxy)- 1 H-inden- 1 - yI)sιianamιnato(2-)-N)tιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the two methyls bound to the titanium are replaced by a single 2-((dιmethylamιno)phenyl)methyl as demonstrated by the following compounds.
(2-((Dιmethylamιno)phenyl)methyl)(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 - (( 1 ,2.3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)tιtanιum
(N-Cyclohexyl- 1 , 1 -dimethy l(2-((dιmethylamιno)pheny l)methyl)- 1 -
(( 1 ,2,3,3a,7a-η)-2-( I -pipeπdinyi)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)tιtamum
(2-((Dιmethylamιno)phenyl)methyl)(N-methyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3.3a,7a-η)- 2-(dιmethylamιno)- 1 H-mden- 1 -y l)sιlanamιnato(2-)-N)tιtanιum
(2-((Dιmethylamιno)pheny l)methyl)(N-ethyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)- 3-methyl-2-(ethylmethylamιno)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)tιtanιum
(2-((Dιmethylamιno)phenyl)methy 1)( 1 , 1 -dimethy l-N-phenyl- 1 -(( 1 ,2,3,3a,7a-η)- 3-methyl-2-(methylphenylamιno)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)tιtanιum
(2-((Dιmethylamιno)phenyl)methyl)( l , l-dιmethyl-N-(phenylmethyl)- l- (( 1 ,2,3,3a,7a-η)-3-methyI-2-(methylphenylamιno)- 1 H-inden- 1 -yl)sιlanamιnato(2-)- N)tιtanιum
(N-Cyclododecyl- 1 , 1 -dιmethyl(2-((dιmethylamιno)phenyl)methy 1)- 1 - (( 1 ,2,3, 3a,7a-η)-3-methyl-2-(methylphenylamιno)- lH-ιnden- l-yl)sιlanamιnato(2-)- N)tιtanιum
(2-((Dιmethylamιno)phenyl)methyl)(N-methyl- 1 , 1-dιmethyl- 1 -(( 1 ,2,3,3a,7a-η)- 2-(dιmethylamιno)-lH-ιnden- l-yl)sιlanamιnato(2-)-N)tιtanιum (2-((Dιmethylamιno)phenyl)methyl)(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 - (( l ,2,3,3a,7a-η)-2-methoxy-lH-ιnden- l-yI)sιlanamιnato(2-)-N)tιtanιum
(2-((Dιmethylamιno)pheny l)methyl)(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 - (( 1 ,2,3,3a,7a-η)-2-((( 1 , 1 -dιmethylethyl)dιmethylsιlyl)oxy)- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)tιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the two methyls bound to the titanium are replaced by π-bound 1 ,4 dιphenyl-l ,3-butadιene as demonstrated by the following compounds.
( 1 , 1 '-(η4- 1 ,3-butadιene- 1 ,4-dιy l)bιs(benzene))(N-( 1 , 1 -Dimethylethyl)- 1 , 1 - dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H-inden- 1 -yl)sιlanamιnato(2-)- N)tιtanιum
( 1 , 1 ' -(η4- 1 ,3-butadιenc- 1 ,4-dιyl )bιs(benzene))(N-Cyclohexy 1- 1 , 1 -dimethy 1- 1 - (( 1 ,2,3,3a,7a-η)-2-( 1 -pipendinyl)- 1 H-mden- 1 -y l)sιlanamιnato(2-)-N)tιtanιum
( 1 , 1 '-(η4- 1 ,3-butadιene- 1 ,4-dιyl)bιs(benzene))(N-Methyl- 1 , 1 -dimethyl- 1 -
(( 1 ,2,3,3a,7a-η)-2-(dιmethylamιno)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)tιtanιum
( 1 ,1 '-(η4- 1 ,3-butadιene- 1 ,4-dιy l)bιs(benzene))(N-Methyl- 1 , 1 -dimethyl- 1 - (( 1 ,2,3,3a,7a-η)-2-(dιethylamιno)- 1 H-inden- 1 -yI)sιlanamιnato(2-)-N)tιtanιum
(1 ,1 '-(η4- 1 ,3-butadιene- 1 ,4-dιyl)bιs(benzene))(N-ethy I- 1 , 1 -Dimethyl- 1 - (( 1 ,2,3,3a,7a-η)-3-methyl-2-(ethylmethylamιno)- 1 H-inden- 1 -yl)sιlanamιnato(2-)- N)tιtanιum
( 1 , 1 '-(η4- 1 ,3-butadιene- 1 ,4-dιyl)bιs(benzene))( 1 , 1 -Dimethyl-N-phenyl- 1 - (( 1 ,2.3, 3a,7a-η)-3-methyl-2-(methylpheny lamino)- l H-ιnden- 1 -yl)sιlanamιnato(2-)- N)tιtanιum ( 1 , T -(η4- 1 ,3-butadιene- 1 ,4-dιyl)bιs(benzene))( 1 , 1 -Dimethyl-N- (phenylmethyl)- 1 -((1 ,2,3,3a,7a-η)-3-methyl-2-(methylphenylamιno)- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)tιtanιum
( 1 , l '-(η4- 1 ,3-butadιene- 1 ,4-dιyl)bιs(benzene))(N-Cyclododecy I- 1 , 1 -dimethyl- l -(( 1 ,2,3, 3a,7a-η)-3-methyI-2-(methylphenylamιno)-lH-ιnden- l-yl)sιlanamιnato(2-)- N)tιtanιum
( 1 , 1 ' -(η4- 1 ,3-butadιene- 1 ,4-dιyl)bιs(benzene))(N-Methyl- 1 , 1 -dimethyl- 1 - (( 1 ,2,3,3a,7a-η)-2-(dιmethylamιno)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)tιtanιum
( 1 , 1 '-(η4- 1 ,3-butadιene- 1 ,4-dιyl)bιs(benzene))(N-( 1 , 1 -Dimethylethyl)- 1 , 1 - dimethyl- 1-(( 1 , 2, 3,3a,7a-η)-2-methoxy-lH-ιnden- l -yl)sιlanamιnato(2-)-N)tιtanιum
( 1.1 ' -(η4- 1 ,3-butadιene- 1 ,4-dιyl)bιs(benzenc))(N-( 1 , 1 -Dimethylethyl)- 1 , 1 - dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-((( 1 , 1 -dιmethylethyl)dιmethylsιlyl)oxy)- 1 H-inden- 1- y!)sιlanamιnato(2-)-N)tιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the two methyls bound to the titanium arc replaced by a π-bound 1 ,3-pentadιene as demonstrated by the following compounds
(N-Cyclohexyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pipendiny 1)- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3-pentadιene)tιtanιum
(N-ethyl- 1 , 1 -Dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-(ethylmethy lamino)- 1 H- inden- 1 -yl)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3-pentadιene)tιtanιum
( 1 , 1 -Dimethyl-N-phenyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-(methylphenylamιno)- IH-inden- 1 -yl)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3-pentadιene)tιtanιum
( 1 , 1 -Dιmethyl-N-(phenylmethyl)- 1 -(( 1 ,2,3.3a.7a-η)-3-methyl-2- (methylphenylamino)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3- pentadιene)tιtanιum (N-Cyclododecy 1- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- ( methy lphenylamino)- 1 H-inden- 1 -y 1 )sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3- pentadιene)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H- inden- 1 -yl)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3-pentadιene)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdinyl)- 1 H- inden- 1 -yl)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3-pentadιene)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2.3.3a,7a-η)-2-(hexahydro- 1H- azepin- 1 -y 1)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3-pentadιene)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1-dιmethyl- 1 -(( 1 ,2,3,3a.7a-η)-2-(hexahydro- 1 (2H)- azocιnyl)- lH-ιnden-l -yl)sιlanamιnato(2-)-N)(( l ,2,3,4-η)- l ,3-pentadιenc)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3 α,7a-η)-2-(octahydro- 1 H- azonin- 1 -yl)(( 1 ,2,3,4-η)- 1 ,3-pentadιene)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(octahydro- 1 (2H)- azecinyl)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3-pentadιene)tιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιmethylamιno)- IH-inden- 1 -yl)(N-( 1 , 1 -dimethylethyl)- 1 , 1 - dιmethyl- l-(sιlanamιnato(2-)-N)(( l ,2,3,4-η)-I ,3-pentadιene)tιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιethylamιno)- 1 H-inden- 1 -yl)(N-( 1 , 1 -dimethylethyl)- 1.1 - dimethyl- 1 -(sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3-pentadιene)tιtanιum
( 1 ,2,3 ,3a,7a-η)-2-(Dιpropy lamino)- 1 H-inden- 1 -yl)(N-( 1 , 1 -dimethylethyl)- 1 , 1- dimethyl- 1 -(sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3-pentadιene)tιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιbutylammo)- 1 H-mden- 1 -yl)(N-( 1 , 1 -dimethylethyl)- 1 , 1 - dιmethyl- l -(sιlanamιnato(2-)-N)(( l ,2,3,4-η)-l ,3-pentadιene)tιtanιum (N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(ethylmethy lamino)- 1 H-inden- 1 -yl)silanaminato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3-pentadiene)titanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2- (methylphenylamino)-l H-inden- 1 -yl)silanaminato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3- pentadiene)titanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2- (methyl(pheny lmethyl)amino)- 1 H-inden- 1 -yl)silanaminato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3- pentadiene)titanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(( 1 , 1- dimethylethyOmethylamino)- 1 H-inden- 1 -yl)silanaminato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3- pentadiene)titanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(methyl( 1 - methylethy l)amino)- 1 H-inden- 1 -yl)silanaminato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3- pentadiene)titanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-
(diphenylphosphino)- 1 H-inden- 1 -yl)silanaminato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3- pentadiene)titanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2- (dimethylphosphino)- 1 H-inden- 1 -y l)silanaminato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3- pentadiene)titanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2- (methylphenylphosphino)- 1 H-inden- 1 -yl )silanaminato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3- pentadiene)titanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(diethylphosphino)- 1 H-inden- 1 -yl)silanaminato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3-pentadiene)titanium (N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(bιs( 1 - methylethyOphosphmo)- 1 H-inden- 1 -yl)sιIanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3- pentadιene)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-methoxy- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3-pentadιene)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-ethoxy- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3-pentadιene)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η )-2-propoxy- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3-pentadιene)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-butoxy- 1 H-inden- 1 - yl)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3-pentadιene)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(( 1 ,1- dimethylethyDoxy)- 1 H-mden- 1 -yl)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3- pentadιene)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-(tπmethylsιloxy)- lH-ιnden-l -yl)sιlanarnιnato(2-)-N)(( l ,2,3,4-η)-l ,3-pentadιene)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-((( 1 , 1- dimethylethyOdimethylsilyOoxy)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η )- 1 ,3- pentadιene)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -methylethoxy )-
1 H-inden- 1 -yl)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3-pentadιene)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-phenoxy- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3-pentadιene)tιtanιum (N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3.3a.7a-η)-2-(pheny lthio)- 1 H- mden- 1 -yl)sιlanammato(2-)-N)(( 1 ,2,3,4-η)- 1 ,3-pentadιene)tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a.7a-η)-2-(methylthιo)- 1 H- ιnden-l-yl)sιlanamιnato(2-)-N)(( l,2,3,4-η)-l,3-pentadιene)tιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the two methyls bound to the titanium are replaced by a π-bound 2,4-hexadιene as demonstrated by the following compounds
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H- mden- 1 -y l)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)-2,4-hexadιene)tιtanιum
(N-Cyclohexyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdinyl)- 1 H-mden- 1 - yl)sιlanamιnato(2-)-N)(( l,2,3,4-η)-2,4-hexadιcne)tιtamum
( 1 ,2,3,3a,7a-η)-2-(Dιmethylamιno)- 1 H-ιnden-1 -yl)(N-methyl- 1 , 1 -dimethyl- 1 - (sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)-2,4-hexadιene)tιtanιum
( 1 ,2,3, 3a.7a-η)-2-(Dιethy lamino)- 1 H-mden- 1 -yl)(N-methyI- 1 , 1 -dimethyl- 1- (sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)-2,4-hexadιene)tιtanιum
(N-ethyl- 1 , 1 -Dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-(ethylmcthylamιno)- 1 H- mden- 1 -yl)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)-2,4-hexadιene)tιtanιum
( 1 , 1 -Dimethyl-N-pheny 1- 1 -(( 1 ,2.3,3a,7a-η)-3-methy l-2-(methy Iphenylamino)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)(( 1 ,2,3,4-η)-2,4-hexadιene)tιtanιum
( 1.1 -Dιmethyl-N-(phenylmethyl)-! -(( 1 ,2,3,3a,7a-η)-3-methyl-2-
(methylphenylamιno)- l H-mden- l-yl)sιlanamιnato(2-)-N)(( l ,2,3,4-η)-2,4- hexadιene)tιtanιum (N-Cyclododecyl- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (methylphenylamino)- IH-inden- l-yl)silanaminato(2-)-N)((l,2,3,4-η)-2,4- hexadiene)tιtanium
( 1 ,2,3,3a,7a-η)-2-(Dimethylamino)-l H-inden- 1 -yl)(N-methyl- 1 , 1 -dimethyl- 1 - (silanaminato(2-)-N)((l,2,3,4-η)-2,4-hexadiene)titanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-methoxy- 1 H-inden- 1 -yl)siianaminato(2-)-N)(( l ,2,3,4-η)-2,4-hexadiene)titanium
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1.2,3,3a.7a-η)-2-((( 1 , 1- dimethylethyl)dimethylsilyl)oxy)- 1 H-inden- 1 -yl)silanaminato(2-)(( 1 ,2,3,4-η)-2,4- hexadiene)titanium
2-Nrheteroatoml-amido-rbridgel-indenyl complexes
In the above names where 2-heteroatom-indenyl complexes are named, a similar range of compounds are those where the dimethylsilyl bridging group is replaced by a diphenylsilyl bridging group as demonstrated by the following compounds.
(N-( 1 , 1 -dimethylethyl)- 1 , 1 -diphenyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H- inden- 1 -yl)silanarninato(2-)-N)dimethyltitanium
(N-( 1 , 1 -dimethylethyl)- 1 , 1 -diphenyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -piperidiny I)- 1 H- inden- 1 -y l)silanaminato(2-)-N)dimethy ititanium
(N-( 1 , 1 -dimethylethyl)- 1 , 1 -diphenyl- 1 -(( 1 ,2,3 ,3a,7a-η)-2-(dimethy lamino)- 1 H- inden- 1 -y l)silanaminato(2-)-N)dimethyltitanium
(N-( 1 , 1 -dimethylethyl)- 1 , 1 -diphenyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-methoxy- 1 H-inden- 1 -yl)silanaminato(2-)-N)dimethyltitanium
(N-( 1 , 1 -dimethylethyl)- 1 , 1 -diphenyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (trimethylsiloxy)- l H-inden- l -yl)silanaminato(2-)-N)dimethyltitanium In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the dimethylsilyl bridging group is replaced by a diisopropoxysilyl bridging group as demonstrated by the following compounds
(N-Butyl- 1 , 1 -bιs( 1 -methylethoxy))- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H- mden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Buty 1-1 , 1 -bιs( l -methylethoxy))- 1-((1 , 2,3,3a,7a-η)-2-( l -pιpeπdιnyl)-lH- den- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Buty I- 1 , 1 -bιs( 1 -methylethoxy))- 1 -(( 1 ,2,3,3a.7a-η)-2-(dιmethy lamino)- 1 H- inden- 1 -y l)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Butyl- 1.1 -bιs( 1 -methylethoxy))- 1 -(( 1 ,2,3,3a,7a-η)-3-methy 1-2-methoxy- 1 H- mden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Butyl- 1 , 1 -bιs( 1 -methylethoxy))- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (tπmethylsιloxy)- lH-ιnden- l-yl)sιlanamιnato(2-)-N)dιmethy Ititanium
In the above names where 2-heteroatom-ιndcnyl complexes are named, a similar range of compounds are those where the dimethylsilyl bridging group is replaced by a dimethoxysilyl bridging group as demonstrated by the following compounds
(N-Cyclohexyl- 1 , 1 -dimethoxy)- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Cyclohexyl- 1 , 1 -dimethoxy)- 1 -(( 1 ,2,3 ,3a,7a-η)-2-( 1 -pipeπdiny 1)- 1 H-inden- l-yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a.7a-η)-2-(Dιmethy lamino)- 1 H-inden- 1 -yl)(N-cyclohexy 1- 1 ,1- dimethoxy)- 1 -(sιlanamιnato(2-)-N)dιmethyltιtanιum (N-Cyclohexyl- 1 , 1 -dimethoxy)- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2-methoxy- 1 H- mden- 1 -yl)sιlanamιnato(2-)-N)dιmethy!tιtanιum
(N-Cyclohexyl- 1 , 1 -dimethoxy)- 1 -(( 1 ,2,3,3a,7a-η)-3-methy!-2- (tπmethylsiloxy)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the dimethylsilyl bridging group is replaced by a ethoxymethylsilyl bndgmg group as demonstrated by the following compounds.
(N-Cyclohexyl- 1 -ethoxy- 1 -methyl)- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H- inden- 1 -y l)sιlanamιnato(2-)-N)dimethyltιtanιum
(N-Cyclohexyl- l-ethoxy-l-methyl)-l-(( l ,2,3,3a.7a-η)-2-( l-pιpeπdιnyI)- l H- inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a,7a-η)-2-(dιmethylamιno)- 1 H-inden- 1 -yl)(N-cyclohexyl- 1 -ethoxy- 1 - methyl)- 1 -(sιlanamιnato(2-)-N)dιmethy!tιtanιum
(N-Cyclohexyl- 1 -ethoxy- 1 -methyl)- 1-(( 1 ,2,3,3a,7a-η)-3-methyl-2-methoxy- lH-ιnden- l -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-Cyclohexyl- 1 -ethoxy- 1 -methyl)- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (tπmethy lsiloxy )- 1 H-inden- 1 -y l)sιlanamιnato(2-)-N)dιmethyltιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the dimethylsilyl bridging group is replaced by a methylphenylsilyl bridging group as demonstrated by the following compounds.
(N-( 1 , 1 -Dimethylethyl)- 1 -methyl- 1 -phenyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 - pyrrolidinyl)- lH-ιnden-l-yl)sιlanamιnato(2-)-N)dιmethyltιtanιum (N-( 1 , 1 -Dimethylethyl)- 1 -methyl- 1 -phenyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 - pipeπdinyO- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιme thy Ititanium
( 1 ,2,3,3a,7a-η)-2-(Dιmethylamιno)- 1 H-inden- 1 -yl)(N-( 1 , 1 -dimethylethyl)- 1 - methyl- 1 -phenyl- 1 -(sιlanamιnato(2-)-N)dιmethy Ititanium
(N-( 1 , 1 -Dimethylethyl)- 1 -methy 1- 1 -phenyl- 1 -(( 1 ,2,3 ,3a,7a-η )-3-methy 1-2- methoxy- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethy Ititanium
(N-( 1 , 1 -Dimethylethyl)- 1 -methyl- 1 -phenyl- 1 -(( 1 ,2,3,3a,7a-η)-3-methyl-2- (trιmethylsιloxy)-l H-ιnden- l-yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the dimethylsilyl bridging gioup is replaced by an ethyl bridging group as demonstrated by the following compounds
(N-( 1 , 1 -Dimethylethy l)-2-(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H-inden- 1 - yl)ethanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dιmethylethyl)-2-(( 1 ,2.3,3a,7a-η)-2-( 1 -pipeπdiny 1)- 1 H-inden- 1 - yl)ethanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιmethy lamino)- 1 H-inden- 1 -yl)(N-( 1 , 1 -dimethy lethy l)-2- (ethanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -DιmethyIethyl)-2-(( 1 ,2,3,3a,7a-η)-3-methyl-2-methoxy- 1 H-mden- 1 - yl)ethanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dιmethylethyl)-2-(( 1 ,2,3,3a,7a-η)-3-methyl-2-(tπmethylsιloxy )- 1 H- inden- 1 -yl)ethanamιnato(2-)-N)dιmethyltιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the dimethylsilyl bridging group is replaced by a tetramethylethyl bridging group as demonstrated by the following compounds (N-( 1 , 1 -Dimethylethy l)-2-(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H-inden- 1 - yl)tetramethylethanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethy lethyl)-2-(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdinyl)- 1 H-inden- 1 - yl)tetramethylethanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιmethylamιno)- 1 H-inden- 1 -yl)(N-( 1 , 1 -dimethy lethyl)-2-
(tetramethylethanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -DιmethylethyI)-2-(( 1 ,2,3,3a,7a-η)-3-methyl-2-methoxy- 1 H-inden- 1 - yl)tetramethylethanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dιmethylethyl)-2-(( 1 ,2,3,3a,7a-η)-3-methy l-2-(tπmethylsιloxy)- 1 H- inden- l -yl)tetramethylethanamιnato(2-)-N)dιmethyltιtanιum
In the above names where 2-heteroatom-ιndenyl complexes arc named, a similar range of compounds are those where the dimethylsilyl bridging group is replaced by a propyl bridging group as demonstrated by the following compounds
(N-( 1 , 1 -Dιmethylethyl)-3-(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H-inden- 1 - yl)propanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dιmethylcthyl)-3-(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdinyl)- 1 H-inden- 1 - yl)propanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a,7a-η)-2-(Dιmethylamιno)- 1 H-inden- 1 -yl)(N-( 1 , 1 -dιmethylethyl)-3- (propanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethy lethyI)-3-(( 1 ,2,3,3a,7a-η)-3-methyl-2-methoxy- 1 H-mden- 1 - y!)propanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dιmethylethyl)-3-(( 1 ,2,3,3a,7a-η)-3-methyl-2-(tπmethy Isiloxy)- 1 H- mden- 1 -yl)propanamιnato(2-)-N)dιmethyltιtanιum In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the dimethylsilyl bridging group is replaced by a methyl bridging group as demonstrated by the following compounds
(N-( 1 , 1 -dιmethylethyl)-3-(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H-inden- 1 - yl)methanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -dιmethylethyl)-3-(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdinyl)- 1 H-inden- 1 - yl)methanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a,7a-η)-2-(dιmethylamιno)- 1 H-inden- 1 -yl)(N-( 1 , 1 -dιmethylethyl)-3- (methanamtnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -dιmethylethyl)-3-(( 1 ,2,3,3a,7a-η)-3-methyl-2-methoxy- 1 H-inden- 1 - yl)methanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -dιmethylethyl)-3-(( 1 ,2,3,3a,7a-η)-3-methyl-2-(tπmethylsιloxy)- 1 H- den- 1 -yl)methanamιnato(2-)-N)dιmethyltιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the dimethylsilyl bridging group is replaced by a dimethylmethyl bridging group as demonstrated by the following compounds
(N-( 1 , 1 -dιmethylethyl)-3-(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H-inden- 1 - yl)dιmethylmethanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -dιmethylethyl)-3-(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdinyl)- 1 H-mden- 1 - yl)dιmethylmethanamιnato(2-)-N)dιmethyltιtanιum
( 1 ,2,3,3a,7a-η)-2-(dιmethylamιno)- 1 H-inden- 1 -yl)(N-( 1 , 1 -dimethy lethyl)-3- (dιmethylmethanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -dιmethylethyl)-3-(( 1 ,2,3,3a.7a-η)-3-methyl-2-methoxy- 1 H-inden- 1 - yl)dιmethylmethanamιnato(2-)-N)dιmethyltιtanιum (N-( 1 , 1 -dιmethyIethyl)-3-(( 1 ,2,3,3a,7a-η)-3-methyl-2-(tπmethylsιloxy)- 1 H- mden- 1 -yl)dιmethylmethanamιnato(2-)-N)dιmethyltιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the dimethylsilyl bridging group is replaced by a dimethylgermanyl bridging group as demonstrated by the following compounds.
(N-( 1 , 1 -dimethylethyl)- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrohdiny 1)-1 H-inden- 1 - yl)dιmethylgermιnato(2-)-N)dιmethy Ititanium
(N-( 1 , 1 -dimethylethyl)- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdmyl)- 1 H-inden- 1 - yl)dιmethylgermιnato(2-)-N)dιmethyltιtanιum
( 1 -(( 1 ,2,3,3a,7a-η)-2-(dιmethylamιno)- 1 H-inden- 1 -yl)(N-( 1 , 1- dιmethylethyl)dιmcthylgermιnato(2-)-N)dιmethy Ititanium
(N-( 1 , 1 -dimethylethyl)- 1 -(( 1 ,2,3,3a,7a-η)-3-methy 1-2-methoxy- 1 H-inden- 1 - yi)dιmethylgermιnato(2-)-N)dιmethy Ititanium
(N-( 1 , 1 -dimethylethyl)- 1 -(( 1 ,2,3,3a,7a-η)-3-methy l-2-(tπmethylsιloxy )- 1 H- mden- 1 -yl)dιmethylgeπτunato(2-)-N)dιmethyltιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the dimethylsilyl bridging group is replaced by a tetramethyldisilyl bridging group as demonstrated by the following compounds
(N-( 1 , 1 -dιmethylethyl)-2-(( 1 ,2,3,3a.7a-η)-2-( 1 -pyrrolidinyl)- 1 H-inden- 1 - yl)tetramethyldιsιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -dιmethylethyl)-2-(( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdinyl)- 1 H-inden- 1 - yl)tetramethyldιsιldnamιnato(2-)-N)dιmethy Ititanium ( 1 ,2,3,3a.7a-η)-2-(dιmethylamιno)- IH-inden- 1 -yl)(N-( 1 , 1 -dιmethy]ethyl)-2- (tetramethyldιsιlanamιnato(2-)-N)dirnethyltιtanιum
(N-( 1 , 1 -dιmethylethyl)-2-(( 1 ,2,3,3a.7a-η)-3-methyl-2-methoxy- 1 H-inden- 1 - yl)tetramethyldιsιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -dimethy lethyl)-2-(( 1 ,2,3 ,3a,7a-η)-3-methyl-2-( tπmethylsiloxy)- 1 H- mden- 1 -y l)tetramethyldιsιlanamιnato(2-)-N)dιmethyltιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the dimethylsilyl bridging group is replaced by a (dιmethylsιlyl)methyl bridging group as demonstrated by the following compounds
(N-( 1 , 1 -dimethylethyl)- 1 -((( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H-inden- 1 - yl)dιmethysιlyl)methanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -dimethylethyl)- 1 -((( 1 ,2,3,3a,7a-η)-2-( I -pipeπdinyl)- 1 H-inden- 1 - yl)dιmethysιlyl)methanamιnato(2-)-N)dιmethyltιtanιum
(1 -((( 1 ,2,3.3a,7a-η)-2-(dιmethylamιno)- 1 H-inden- 1 -yl)dιmethysιlyl)(N-( 1 , 1- dιmethylethyl)methanamιnato(2-)-N)dιrnethyltιtanιum
(N-( 1 , 1 -dimethylethyl)- 1 -((( 1 ,2,3,3a,7a-η)-3-methyl-2-methoxy- 1 H-inden- 1 - yl)dιmethysιlyl)methanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -dimethylethyl)- 1-((( 1 ,2,3 ,3a,7a-η)-3-methyl-2-(tπmethyisιloxy)- lH- inden- 1 -yl)dιmethysιlyl)methanamιnato(2-)-N)dιmethyltιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the dimethylsilyl bridging group is replaced by a (methyl)dιmethylsιlyl bridging group as demonstrated by the following compounds. (N-( 1 , 1 -dimethylethyl)- 1 -((( 1 ,2,3,3a,7a-η)-2-( 1 -pyrrolidinyl)- 1 H-inden- 1 - yl)methyl)dιmethylsιlylamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -dimethylethyl)- 1 -((( 1 ,2,3,3a,7a-η)-2-( 1 -pipeπdiny 1)- 1 H-inden- 1 - yl)methyl)dιmethylsιlylamιnato(2-)-N)dιmethyltιtanιum
( 1 -((( 1 ,2,3,3a,7a-η)-2-(dιmethylamιno)- 1 H-inden- 1 -yl)methy l)(N-( 1 , 1 - dιmethylethyl)dιmethylsιIylamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -dimethylethyl)- 1 -((( 1 ,2,3 ,3a,7a-η)-3-methy 1-2-methoxy- 1 H-inden- 1 - yl)methyl)dιmethylsιlylamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 ,1 -dimethylethyl)- 1 -((( 1 ,2,3,3a,7a-η)-3-methyl-2-(tπmethylsιloxy)- 1H- inden- l-yl)methyl)dιmethylsιlylamιnato(2-)-N)dιmethyltιtanιum
2-N-heteroatom-amιdo-rιndenyll complexes
In the above names where 2-hetcroatom-ιndenyl complexes arc named, a similar range of compounds are those where the 2-heteroatom-ιndenyl moeity is replaced by an alkyl or aryl substituted 2-heteroatom-ιndenyl group as demonstrated by the following compounds
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-5-ethyl-6-methy l-2-( 1 - pyrrolidinyl)- 1 H-mden- l -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1-(( 1 ,2,3,3a,7a-η)-5-ethy l-6-methy l-2-( 1 - pipeπdiny 1)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 -(( 1 ,2,3,3a,7a-η)-5-Ethyl-6-methyI-2-(dιmethylammo)- 1 H-inden- 1 -yl)(N-
( 1 , 1 -dimethylethyl)- 1 , 1 -dιmethylsιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1-(( 1 ,2,3,3a,7a-η)-5-ethy l-6-methyl-3- methyl-2-methoxy- 1 H-inden- 1 -yl)sιianamιnato(2-)-N)dιmethyltιtanιum (N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1-(( 1 ,2,3.3a,7a-η)-5-ethyl-6-methyl-3- methyl-2-(tπmethylsιloxy)-l H-ιnden-l -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3.3a.7a-η)-4,6-dιmethyl-2-( 1 - pyrrolidinyl)- lH-ιnden- l-yl)sιlanarnιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1-Dιmethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-4,6-dιmethyl-2-( 1 - pipeπdinyl)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 -(( 1 ,2,3,3a,7a-η)-4,6-Dιmethyl-2-(dιmethylamιno)- 1 H-inden- 1 -yl)(N-( 1 , 1- dimethylethyl)- 1 , 1 -dιmethylsιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3,4,6-tπmethyl-2- methoxy- 1 H-inden- 1 -y l)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-3,4,6-tπmethyl-2- (tπmcthylsιloxy)-l H-ιnden- l -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-4-phenyl-2-( 1 - pyrrolidinyl)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-4-pheny l-2-( 1 - pipeπdiny 1)- 1 H-inden- 1 -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 -(( 1 ,2 3.3a,7a-η)-4-Pheny l-2-(dιmethyiamιno)- 1 H-inden- 1 -y l)(N-( 1 , 1 - dimethylethyl)- 1 , 1 -dιmethylsιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1-DιmethylethyO- 1 , 1 -dimethyl- 1-(( 1 ,2,3,3a,7a-η)-4-phenyl-2-methoxy- lH-ιnden-l -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-4-phenyl-2- (tπmethylsιloxy)-lH-ιnden-l-yl)sιlanamιnato(2-)-N)dιmethyltιtanιum (N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1-(( 1 ,2,3,3a,9a-η)-5,6,7.8-tetrahydro- 3,5,5,8,8-pentamethyl-2-( 1 -pyrrolidinyl)- 1 H-benz(f)mden- 1 -yl)sιlanamιnato(2-)- N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,9a-η)-5,6,7,8-tetrahydro- 5,5,8,8-tetramethyl-2-( 1 -pyrrolidinyl)- 1 H-benz(f)ιnden- 1 -yl)sιlanamιnato(2-)- N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a.8a-eta)- 1 ,5,6,7-tetrahydro-3- methyl-2-( l-pyrrolιdιnyl)-s-ιndacen- l-yl)sιlanamιnato(2-)-N-dιmethyl-tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,8a-eta)- 1 ,5,6,7-tetι ahydro-2- ( l -pyrrolιdιnyl)-s-ιndacen-1-yl)sιlanamιnato(2-)-N-dιmethyl-tιtanιum
In the above names where 2-heteroatom-ιndenyl complexes are named, a similar range of compounds are those where the 2-heteroatom-ιndenyl moeity is replaced by an alkyl or aryl substituted cyclopentadienyl group as demonstrated by the following compounds
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-4,5.6,7-tetrahydro-2-
( 1 -pyrrolidinyl)- lH-ιnden- l -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-4,5,6,7-tctrahydro-2- ( 1 -pipeπdinyl)- 1 H-inden- 1 -y l)sιlanamιnato(2-)-N)dιmethy Ititanium
( 1 -(( 1 ,2,3,3a,7a-η)-4,5,6,7-tetrahydro-2-(dιmethylamιno)- 1 H-mden- 1 -yl)(N- ( 1 ,1 -Dimethylethyl)- 1 , 1 -dιmethylsιlanamιnato(2-)-N)dιmethy!tιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-4,5,6,7-tetrahydro-3- methyl-2-methoxy- IH-ιnden-l-yl)sιlanamιnato(2-)-N)dιmethyltιtanιum
(N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-4,5,6,7-tetrahydro-3- methyl-2-(tπmethylsιloxy)-l H-ιnden- l -yl)sιlanamιnato(2-)-N)dιmethyltιtanιum ( 1 -(( 1 ,2,3,4,5-η)-2-Dιmethylamιno)-3-methyl-2,4-cyclopentadιen- 1 -yl)-N-( 1 , 1- dimethyethyl)- 1 , 1 -dιmethylsιlanarnιnato(2-)-N)dιmethyltιtanιum
( 1 -((1 ,2,3,4,5-η)-2-Dιmethylamιno)-2,4-cyclopentadιen- 1 -yl)-N-( 1 , 1 - dimethyethyl)- 1 , 1 -dιmethylsιlanamιnato(2-)-N)dιmethyltιtanιum
( l-(( l,2,3,4,5-η)-3-Dιmethylamιno)-3-methyl-2.4-cyclopentadιen-l-yl)-N- cyclohexyl- 1 , 1 -dιmethylsιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 -(( 1 ,2,3,4,5-η)-2-Dιmethylamιno)-2,4-cyclopentadιen- 1 -yl)-N-cyclohexyl- 1 , 1 -dιmethylsιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 -(( 1.2,3,4,5-η)-2-Methoxy)-3-methyl-2,4-cycloρentadιen- 1 -yl)-N-( 1 , 1- dimethyethyl)- l , l -dιmethylsιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 -(( 1 ,2,3,4,5-η)-2-Methoxy)-2,4-cyclopentadιen- 1 -yl)-N-( 1 , 1 -dimethyethyl)- 1 , 1 -dιmethylsιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 -(( 1 ,2,3,4,5-η)-2-Methoxy)-3-methyl-2,4-cyclopentadιcn- 1 -yl)-N-cyclohexyl- 1 , 1 -dιmethylsιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 -(( 1 ,2,3,4,5-η)-2-Methoxy)-2,4-cyclopentadιen- 1 -yI)-N-cyclohexyl- 1 , 1 - dιmethylsιlanamιnato(2-)-N)dιmethy Ititanium
( 1 -(( 1 ,2,3,3a,6a-η)-2-(Dιmethylamιno)- 1 ,4,5,6-tetrahydro- 1 -pentalenyO-N- ( 1 , 1 -dimethylethyl)) 1 , 1 -dιmethylsιlanamιnato(2-)-N)dιmethy Ititanium
( 1 -(( 1 ,2,3,3a,6a-η)-2-(Dιmethylamιno)- 1 ,4,5,6-tetrahydro- l-pentalenyl)-N- cyclohexyl) 1 , l-dιmethylsιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 -(( 1 ,2,3,3a,6a-η)-2-(methoxy)- 1 ,4,5,6-tetrahydro- 1 -pentalenyl)-N-( 1 , 1- dimethylethyl)) 1 , 1 -dιmethylsιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 -(( 1 ,2,3,3a,6a-η)-2-(methoxy)-l ,4,5,6-tetrahydro- 1 -pentalenyl)-N- cyclohexy 1) 1 , 1 -dιmethylsιlanamιnato(2-)-N)dιmethyltιtamum ( 1 -(( 1 ,2,3,3a.6a-η)-2-(Tπmethylsιloxy)- 1 ,4,5,6-tetrahydro- 1 -pentalenyl)-N- ( 1 ,1 -dimethylethyl)) 1 , 1 -dimethy lsιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 -(( 1 ,2,3,3a,6a-η)-2-(Tπmethylsιloxy)- 1 ,4,5,6-tetrahydro- 1 -ρentalenyl)-N- cyclohexyl) 1 , 1 -dιmethylsιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 -(( 1 ,2,3,3a,6a-η)-2-(Tπmethylsιloxy )- 1 ,4,5,6-tetrahydro- 1 -pentalenyl)-N-
( 1 , 1 -dimethylethyl)) 1 , 1 -dιmethylsιlanamιnato(2-)-N)dιmethyltιtanιum
( 1 -(( 1.2,3,3a,6a-η)-2-(Tπmethylsιloxy)- 1 ,4,5,6-tetrahydro- 1 -pentalenyl)-N- cyclohexyl) 1 , 1 -dιmethylsιlanamιnato(2-)-N)dιmethyltιtanιum
The complexes can be prepared by use of well known synthetic techniques Optionally a reducing agent can be employed to produce the lower oxidation state complexes Such a process is disclosed in USSN 8/241 ,523, filed May 13, 1994, published as WO 95/00526, the teachings of which are hereby incorporated by reference The reactions are conducted in a suitable noninterfeπng solvent at a temperature from -100 to 300°C, preferably from -78 to 100°C, most preferably from 0 to 50°C By the term "reducing agent" herein is meant a metal or compound which, under reducing conditions causes the metal M, to be reduced from a higher to a lowei oxidation state Examples of suitable metal reducing agents are alkali metals, alkaline earth metals, aluminum and zinc, alloys of alkali metals or alkaline earth metals such as sodium/mercury amalgam and sodium/potassium alloy Examples of suitable reducing agent compounds are sodium naphthalenide, potassium graphite, lithium alkyls, lithium or potassium alkadienyls, and Gπgnard reagents Most preferred reducing agents are the alkali metals or alkaline earth metals, especially lithium and magnesium metal
Suitable reaction media for the formation of the complexes include aliphatic and aromatic hydrocarbons, ethers, and cyclic ethers, particularly branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof, cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, aromatic and hydrocarbyl-substituted aromatic compounds such as benzene, toluene, and xylene, C [_4 dialkyl ethers, C j _4 dialkyl ether derivatives of (poly)alkylene glycols, and tetrahydrofuran. Mixtures of the foregoing are also suitable
One synthesis of heteroatom-substituted cyclopentadienyl systems, which are useful as precursors to constrained geometry catalyst systems (CGC), is depicted in Scheme 1 , below, where:
a.) excess amine, MeOH, 25 °C (-H2O);
b. ) excess am e (8 eq), T1CI4 ( 1 eq) in CH2CI9, 0 °C, then add ketone and warm to 25 °C;
c.) 1.05 eq n-BuLi/ hexane at 25 °C; d.) 1 0- 1 5 eq Cl-silane THF at 25 °C, e ) 2.05 eq n-BuLi/ hexane at 25 °C; and
R, R' , R", R"\ R"" independently selected in each case are H (except on the nitrogen bound directly to the cyclopentadienyl ring), alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, and are not limited only to these groups
Scheme
Figure imgf000055_0001
©
Li
ketone enamine
Figure imgf000055_0002
CGC-ligand
Figure imgf000055_0003
CGC-ligand CGC-dianion
The heteroatom-containing substituent has a nitrogen in the 2-posιtιon of the indenyl system. 2-Indanone is a convenient starting material for conversion to the corresponding enamine, although formation of the latter is not restricted to the use of this compound. Enamines of indanone are typically formed by methods known in the art, including condensation of secondary amines with the ketone in anhydrous alcohol (U. Edlund Acta Chemica Scandinavica, 1974, 27, 4027-4029). Typically, enamines of 2-ιndanone are more easily formed by amine condensation than 1 -indanone analogues. With more steπcally hindered ketones , such as l -methyl-2-ιndanone or more volatile amines such as dimethyl amine, it may be preferable to employ stronger dehydrating reagents such as titanium chloroamides (generated in situ from titanium tetrachloπde and the condensation amine) (R. Carlson, A Nilsson Acta Chemica Scandinavica B 38, 1984, 49-53). These two methods have been employed to produce enamines substituted in the 2-posιtιon of the indene (the 1 -position is typically bonded to a silicon or other linking moiety in subsequent compounds). Another method for the preparation of enamines involves electrophilic amination of carbanions such as lithium indenide (E. Erdik, M, Ay Chem Rev.. 1989, 89, 1947- 1980)
For subsequent formation of highly pure CGC-hgands, enamines prepared by these routes must be highly pure and free of ketone, Aldol by-products and higher weight reaction tars which typically accompany product formation. None of the aforementioned routes uniformly provides a product which can be used without some sort of further purification We have found that chromatographic purification using flash-grade silica gel or alumina rapidly promotes hydrolysis of the enamine to free amine and ketone, an unfortunate consequence. Although these compounds are highly water and air sensitive, enamines of this nature may be purified by careful fractional distillation, or occasionally, recrystallization. In particular, rapid distillation of indanone enamines is required to prevent thermal polymerization in the still at elevated temperature. Expedient conversion of pure enamine to its corresponding anionic salt is required to obtain a highly pure CGC-ligand, since enamines may also be photochemically sensitive 2-Indanone is also a preferred starting material for CGC-ligands substituted with oxygen in the 2-position, as shown in Scheme 2, below, where:
a.) alcohol, benzene, reflux (-H2O); b.) 1.05 eq n-BuLi/ hexane at 25 °C; c.) 1.0- 1.5 eq Cl-silane THF at 25 °C; d.) 2.05 eq n-BuLi/ hexane at 25 °C; and
R, R', R", R'", R"" independently selected in each case are H (except on oxygen), alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, and are not limited only to these groups.
Scheme 2
Figure imgf000058_0001
ketone enol ether enol ether anion
Figure imgf000058_0002
CGC-ligand
Figure imgf000058_0003
CGC-ligand CGC-dianion In particular, enol ethers in this position can be made by dehydration of the appropriate hemiketal which is formed in situ from indanone and alcohol in the piesence of an acidic catalyst (L A Paquette, A Varadarajan, E Bey J Am Chem Soc 1984, 106, 6702-6708, W E Parham, C D Wright J Org Chem 1957, 22, 1473-77) Silyl enol ethers can be made by forming the enolate of 2-ιndanone and quenching with, for example, t-butyl-dimethylsilyl chloride (R Leino, H Luttikhedde C E Wilen, R Sillanpa, J H Nasman, Organometallics, 1996, 15, 2450-2453) Enol ethers of indanones, like the enamine analogues, are also susceptible to hydrolysis and are very oxygen sensitive Once purified, they are best expediently converted to their corresponding anionic salts
Once highly purified, conversion of the enamine to its corresponding anionic salt may be accomplished by reaction with an appropriate base of suitable strength in an appropriate noninteifeπng solvent Under appropriate, anaerobic, anhydrous conditions, the often solid anionic salt may be filtered, washed and dried in nearly quantitative yield Likewise, enol ethers of 2-ιndanone can be deprotonated to the corresponding anionic salt The choice of suitable base is more restricted in the case of silyl enol ethers, since certain bases, like n-butyllithium, were found to cause desilylation with generation of the enolate anion (base attack on the silyl group)
The formation of constrained geometry ligands (CGC-ligand) based upon heteroatom-substituted mdenes is based upon the anion alkylation method described by Nickias and coworkers (Nickias, Peter N , Devore, David D , Wilson, David R PCT Int Appl , WO 9308199 A 1 930429 CAN 1 19 160577, Carpenetti, Donald W , Kloppenburg, Lioba, Kupec, Justin T , Petersen, Jeffrey L Organometallics 1996, 15(6), 1572-81 ) in which a cyclopentadienyl anion is reacted with electrophiles such as halogenated secondary alkylamines or halogenated secondary silylamines to give the corresponding cyclopentadienyl alkylamine or cyclopentadienyl silylamme Under halogenated secondary alkylamines or halogenated secondary silylamines are included for example (t-butyθ(chlorodιmethylsιlyl)amιne, (t- butyl)(chlorodιmethylsιlylmethyl)amιne, (t-buty (bromomethyldιmethylsιlyl)amιne, (t-butyl)(2-chloroethyl)amιne, (chlorodιmethylsιly (phenyl)amιne, (adamantyθ(chlorodiphenylsilyl)amine, (chiorodimethylsily (cyclohexyl)amine, (benzyθ(chlorodimethylsilyl)amine and (t-buty (chloromethylphenylsilyl)amine. For example, dropwise addition of the lithio derivative of the anionic salt in THF to a molar excess of (t-butyl)(chlorodimethylsilyl)amine in THF followed by standard removal of lithium chloride and excess electrophile often provides highly pure ligand which may be subsequently used without further purification. This so-called CGC- ligand may be converted to its insoluble dianionic salt by reaction of the free base with two equivalents of a base of suitable strength in an appropriate noninterfering solvent.
By appropriate noninterfering solvent in the context of the present invention is meant a solvent that doesn't interfere with the formation of, or react deleteriously with, the desired product. Such solvents suitable for the preparation of the anionic salts and dianionic salts of the invention include, but are not limited to aliphatic and aromatic hydrocarbons, particularly straight and branched chain hydrocarbons such as butane, pentane, hexane, heptane, octane, decane, including their branched isomers and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyciohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; aromatic and hydrocarbyl-substituted aromatic compounds such as benzene, toluene, xylene, ethylbenzene, diethylbenzene and mixtures thereof; ethers and cyclic ethers, particularly Cj .g dialkyl ethers, such as diethyl ether, dibutyl ether and methyl-t-butyl ether, C i _6 dialkyl ether derivatives of (poly)alkylene glycols, such as dimethoxyethane, and dioxane and THF and mixtures thereof. Mixtures of the foregoing are also suitable.
Bases of suitable strength for the preparation of the dianionic salts of the invention include hydrocarbyl salts of Group 1 and Group 2 metals, especially alkyl or aryl salts of lithium or magnesium, such as methyllithium, ethyllithium, n- butyllithium, s-butyllithium, t-butyllithium, phenyllithium, methyl magnesium chloride, ethyl magnesium bromide, i-propyl magnesium chloride, dibutylmagnesium, (butyl)(ethyl)magnesium, dihexylmagnesium; Group 1 or Group 2 metals, such as lithium, sodium, potassium and magnesium; Group 1, Group 2 or Group 13 metal hydrides, such as lithium hydride, sodium hydride, potassium hydride or lithium aluminum hydride. Group 1 or Group 2 metal amide complexes, such as lithium diisopropylamidc, lithium dimethylamide, lithium hexamethyldisilazide, sodamide and magnesium diisopropylamidc
Bases of suitable strength for the preparation of the anionic salts of the invention include the foregoing as well as Group 1 or Group 2 metal alkoxide complexes, such as sodium ethoxide, sodium t- butoxide, potassium butoxide and potassium amylate
The metallation of the dianionic salt may be accomplished by methods cited in this art as well. Reaction of the dianionic salt in THF with TiCl3 (THF followed by oxidation with methylene chloride or lead dichloπde is a well established procedure (J. Okuda, S. Verch, T. P. Spaniol, R. Stur er Chem. Ber., 1996, 129, 1429- 1431, D. D Devore EP 514,828) which affords the titanium (IV) dichloπde complex. The dichloπde may be silylated or hydrocarbylated by ligand exchange with an appropriate silylating or hydrocarbylating agent, such as methyllithium, methyl magnesium chloride, benzyl potassium, allyl lithium, tπmethyisilylmethyl lithium, neopentyl magnesium bromide and phenylhthium. A more complete list of appropriate silylating or hydrocarbylating agents is given below.
A general method for producing the tιtanιum(II) diene complex from the corresponding tιtanιum(IV) dichloπde has been described by Devore and coworkers (D. D. Devore, F. J Timmers, D. L. Hasha, R. K. Rosen, T. J. Marks, P. A. Deck, C L. Stern, Organometallics, 1995, 14, 3132-3134; D. D. Devore, F. J. Timmers, J. C. Stevens, R. D. Mussell, L. H. Crawford, D. R. Wilson, US 5.556,928). Thus, treatment of the dichloride with n-butyl lithium in the presence of an appropriate diene produces the analogous titanium (II) diene complex for heteroatom-substituted systems.
The formation of the CGC metal (III) complexes according to the invention can be accomplished by any of several synthesis methods, among which are the following: The reaction under anaerobic and anhydrous conditions of the dianionic salts with tπvalent metal salts, such as Group 4 metal (III) halide or alkoxide complexes, can be carried out, optionally followed by silylation or hydrocarbylation with suitable silylating or hydrocarbylating agents, to form the corresponding CGC metal (III) halide, alkoxide, silyl or hydrocarbyl complexes of the invention
A further synthesis method involves reducing an appropriate CGC metal (IV) dihahde or dialkoxide complex, or, preceded by monosilylation or monohydrocarbylation, the corresponding CGC (IV) silyl or hydrocarbyl monohalide or monoalkoxide complex with a suitable reducing agent to the corresponding CGC metal (III) halide, alkoxide, silyl or hydrocarbyl complex
Found to be particularly suitable in the synthesis of the CGC metal (III) complexes according to the present invention are the methods described by Wilson (D R Wilson US 5,504,224, 1996) which is incorporated herein by reference For example, cyclopentadienyl ligands can be displaced by the dianionic salts and/or by the (stabilizing) hydrocarbylating agents from cyclopentadienyl-containing Group 4 metal complexes m the +3 oxidation state to give the CGC metal (III) complexes of the invention
Suitable reducing agents for reducing the oxidation state of the metals of the CGC metal (IV) complexes from +4 to +3 have been described above and especially include zinc, aluminum and magnesium
Suitable silylating and hydrocarbylating agents for the CGC metal (III) complexes and the CGC metal (IV) complexes of the invention include alkyl, such as methyl, ethyl, propyl, butyl, neopentyl and hexyl, aryl, such as phenyl, naphthyl and biphenyl, aralkyl, such as benzyl, tolylmethyl, diphenylmethyl; alkaryl, such as tolyl and xylyl, allyl, silyl- or alkyl-substituted allyl, such as methylallyl, tπmethylsilylallyl, dimethylallyl and tπmethylallyl, tπalkylsilyl, such as tπmethylsilyl and tπethylsilyl, tπalkylsilylalkyl, such as tπmethylsilylmethyl, pentadienyl, alkyl- or silyl-substituted pentadienyl, such as methylpentadienyl, dimethylpentadienyl, tπmethylsilylpentadienyl, bιs(tπmethylsιlyl)pentadιenyl, cyclohexadienyl and dimethylcyclohexadienyl. dialkylaminoalkaryl, such as o-(N,N- dimethylaminomethyOphenyl; and dialkylammoaralkyl, such as o-(N,N- dimethylamino)benzyl; salts of Group 1 , 2 or 13 metals, preferably the salts of lithium, sodium, potassium, magnesium and aluminum. Preferred silylating and hydrocarbylating agents include trimethylaluminum, methyllithium, methyl magnesium chloride, neopentyllithium, trimethylsilylmethyi magnesium chloride and phenyllithium. Stabilizing group-containing hydrocarbylating agents are also included, especially the stabilizing group-containing hydrocarbylating agents and salts of the stabilizing group-containing hydrocarbyl groups described in US 5,504,224, whose salts include, for example, benzyl potassium, 2-(N,N-dimethylamino)benzyllithium, allyllithium and dimethylpentadienyl potassium. The stabilizing groups are further described in U.S. Ser. No. 8003, filed Jan. 21 , 1993 (corresponding to WO 93/19104), incorporated herein by reference.
Preferred halides or alkoxides of the metal (III) halide or alkoxide complexes and the CGC metal (III) halide or alkoxide complexes include fluoride, chloride, bromide, iodide, methoxide, ethoxide, i-propoxide, n- propoxide, butoxide and phenoxide. Preferred metal (III) halide or alkoxide complexes include titanium (III) chloride, titanium (III) ethoxide, titanium (III) bromide, titanium (III) isopropoxide, titanium (III) (dichloro)(isopropoxide), as well as Lewis base complexes of the foregoing, especially ether complexes thereof, particularly diethyl ether, tetrahydrofuran and ethylene glycol dimethyl ether complexes thereof. Preferred cyclopentadienyl-containing Group 4 metal complexes in the +3 oxidation state include triscyclopentadienyl titanium, biscyclopentadienyl titanium chloride, biscyclopentadienyl titanium bromide, biscyclopentadienyl titanium isopropoxide, cyclopentadienyl titanium dichloride, cyclopentadienyl titanium diphenoxide, cyclopentadienyl titanium dimethoxide and bis((trimethylsilyl)(t- butyl )cyclopentadienyl)zirconium chloride.
The ligands of this invention are 2-heteroatom substituted cyclopentadienyl- containing ligands where the ligand is in the form of:
(A) a free base with 2 protons capable of being deprotonated;
(B) a dilithium salt; (C) a magnesium salt: or
(D) a mono or disilylated dianion.
Within the scope of this invention is the use of a ligand of this invention for synthesis to produce a metal complex of this invention, or for synthesis to produce a metal complex comprising a metal from one of Groups 3 to 13 of the Periodic Table of the Elements, the ianthanides or actinides, and from 1 to 4 of the ligands.
The ligands of this invention may be used in various forms, including salts, with various groups attached at the Z position in syntheses leading to metal complexes in which the metal is from Groups 3-16 of periodic table or the Ianthanides, and in which from one to four of these ligands, alone or in combination with other ligands, are present in the metal complex. The methods of synthesis may be similar or analogous to those discussed herein for the Group 4 metal complexes of this invention, as well as various other synthetic procedures known in the art. The metal complexes are useful as catalysts in various reactions, including olefin polymerization reactions.
Obviously, naming of these metal complexes, as well as the neutral ligands and various intermediates is complicated and challenging, and the rules in various systems for these names are evolving. Therefore, reference to the structural representations is recommended. Generally, with attachment of the bridge of a constrained geometry complex or of a bridged bis-Cp complex in the 1 -position, the heteroatom then is in the 2-position. The structural representations herein should not be given a strictly literal interpretation with regard to bond orders, bond lengths or strengths. For example, the X-ray data show that the N-Cp bonds of some complexes are shorter than would be expected for a single bond, which indicates at least some double bond character in the N-Cp bond.
Within the scope of the above discussion relating to ligands, preferred ligands of this invention correspond to the formula:
Figure imgf000065_0001
where x is 0 or 1 , y is 0 or 1 , z is 0 or 1 , x + y is 0 or 1 , x + z is 0 or 1, and the other symbols are as previously defined, where the dotted circle within the Cp ring implies the various possibilities for double bond character, partial double bond character or aromatic character as appropriate, depending upon the values for x, y, and z
The complexes are rendered catalytically active by combination with an activating cocatalyst or by use of an activating technique. Suitable activating cocatalysts for use herein include polymeric or oligomeric alumoxanes, especially methylalumoxane, tπisobutyl aluminum modified methylalumoxane, or lsobutytalumoxane; neutral Lewis acids, such as C 1.45 hydrocarbyl substituted Group
13 compounds, especially tπ(hydrocarbyl)alumιnum- or tπ(hydrocarbyl)boron compounds and halogenated (including perhalogenated) derivatives thereof, having from 1 to 15 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluoπnated tπ(aryl)boron compounds, and most especially tns(o- nonafluorobιphenyl)borane, tπs(pentafluorophenyl)borane, nonpolymeπc, compatible, noncoordinating, ion forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium-, phosphonium-, oxonium-, carbonium-, silyhum- or sulfonium- salts of compatible, noncoordinating anions, or ferrocenium salts of compatible, noncoordinating anions; bulk electrolysis (explained in more detail hereinafter), and combinations of the foregoing activating cocatalysts and techniques The foregoing activating cocatalysts and activating techniques have been previously taught with respect to different metal complexes in the following references EP-A-277,003, U.S -A-5, 153, 157, U S -A-5,064,802, EP-A-468,651 (equivalent to U.S Serial No 07/547,718), EP-A-520,732 (equivalent to U S. Seπal No 07/876,268). and EP-A-520,732 (equivalent to U S Seπal No 07/884,966 filed May 1 , 1992), the teachings of which are hereby incorporated by reference
Combinations of neutral Lewis acids, especially the combination of a tπalkyl aluminum compound having from 1 to 4 carbons in each alkyl group and a halogenated tπ(hydrocarbyl)boron compound having from 1 to 20 carbons in each hydrocarbyl group, especially tπs(pentafluorophenyl)borane, tπs(o- nonafluorobiphenyOborane, further combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tπs(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane are especially desirable activating cocatalysts A benefit according to the present invention is the discovery that the most efficient catalyst activation using such a combination of tπs(pentafluorophenyl)borane/alumoxane mixture occurs at reduced levels of alumoxane Preferred molar ratios of Group 4 metal complex tπs(pentafluorophenyl)borane alumoxane are from 1 1 1 to I 5 5, more preferably from 1 1 1 5 to 1 5 3 The surprising efficient use of lower levels of alumoxane with the present invention allows for the production of olefin polymers with high catalytic efficiencies using less of the expensive alumoxane cocatalyst Additionally, polymers with lower levels of aluminum residue, and hence greater clarity, are obtained
Suitable ion forming compounds useful as cocatalysts in one embodiment of the present invention comprise a cation which is a Bronsted acid capable of donating a proton, and a compatible, noncoordinating anion, A As used herein, the term "noncoordinating" means an anion or substance which either does not coordinate to the Group 4 metal containing precursor complex and the catalytic derivative derived therefrom, or which is only weakly coordinated to such complexes thereby remaining sufficiently labile to be displaced by a neutral Lewis base A noncoordinating anion specifically refers to an anion which when functioning as a charge balancing anion in a cationic metal complex does not transfer an anionic substituent or fragment thereof to said cation thereby forming neutral complexes "Compatible anions" are anions which are not degraded to neutrality when the initially formed complex decomposes and are noninterfeπng with desired subsequent polymerization or other uses of the complex
Preferred anions are those containing a single coordination complex comprising a charge-bearing metal or metalloid core which anion is capable of balancing the charge of the active catalyst species (the metal cation) which may be formed when the two components are combined Also, said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nitπles. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom arc, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially
Preferably such cocatalysts may be represented by the following general formula
Figure imgf000067_0001
wherem:
L* is a neutral Lewis base, (L*-H)+ is a Bronsted acid, ( )d- is a noncoordinating, compatible anion having a charge of d-, and d is an integer from 1 to 3
More preferably (A)d- corresponds to the formula. [MO4] ,
wherein-
M' is boron or aluminum in the +3 formal oxidation state; and
Q independently each occurrence is selected from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halosubstituted-hydrocarbyl, halosubstituted hydrocarbyloxy, and halo- substituted silylhydrocarbyl radicals (including perhalogenated hydrocarbyl- perhalogenated hydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Q having up to 20 carbons with the proviso that in not more than one occurrence is Q halide. Examples of suitable hydrocarbyloxide Q groups are disclosed in U.S. Patent 5,296,433, the teachings of which are herein incorporated by reference.
In a more preferred embodiment, d is one, that is, the counter ion has a single negative charge and is A". Activating cocatalysts comprising boron which are particularly useful in the preparation of catalysts of this invention may be represented by the following general formula:
(L*-H)+(BQ4)-;
wherein:
L* is as previously defined;
B is boron in a formal oxidation state of 3; and
Q is a hydrocarbyl-, hydrocarbyloxy-, fluoπnated hydrocarbyl-, fluoπnated hydrocarbyloxy-, or fluoπnated silylhydrocarbyl- group of up to 20 nonhydrogen atoms, with the proviso that in not more than one occasion is Q hydrocarbyl.
Most preferably, Q is each occurrence a fluoπnated aryl group, especially, a pentafluorophenyl group.
Illustrative, but not limiting, examples of ion forming compounds comprising proton donatable cations which may be used as activating cocatalysts in the preparation of the catalysts of this invention are tπ-substituted ammonium salts such as: tπmethylammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, tπethylammonium tetraphenylborate, tπpropylammonium tetraphenylborate, tπ(n-butyl)ammonιum tetraphenylborate, methyltetradecyloctadecylammonium tetraphenylborate,
N,N-dιmethylanιlιnιum tetraphenylborate,
N,N-dιethylanιlιnιum tetraphenylborate, N,N-dιmethyl(2,4,6-tπmethylanιlιnιum) tetraphenylborate, tπmethylammonium tetrakιs(penta-fluorophenyl)borate, tπethylammomum tetrakιs(pentafluorophenyl)borate, tπpropylammonium tetrakιs(pentafluorophenyl)borate, tπ(n-butyl)ammonιum tetrakιs(pentafluorophenyl)borate, tπ(sec-butyl)ammonιum tetrakιs(pentafluorophenyl)borate,
N,N-dιmethylanιlιnιum tetrakιs(pentafluorophenyl)borate,
N,N-dιethylanιlιnιum tetrakιs(pentafluorophenyl)borate,
N.N-dimethy 1(2,4.6-tπmethylanιlιnιum) tetrakιs(pentafluorophenyl)borate tπmethylammonium tetrakιs(2,3,4,6-tetrafluorophenyl)boratc, tπethylammonium tetrakιs(2,3,4,6-tetrafluorophenyl)borate, tπpropylammonium tetrakιs(2,3,4,6-tetrafluorophcnyl)borate, tπ(n-butyl)ammonιum tetrakιs(2,3,4,6-tetrafluorophenyl)borate, dimethy l(t-butyl)ammonιum tetrakιs(2.3,4,6-tetraπuorophenyl)boratc,
N,N-dιmethylanιlιnιum tetrakιs(2,3,4,6-tetrafluorophenyl)borate, N,N-dιethylanιhnιum tetrakιs(2,3 4,6-tetrafluorophenyl)borate, and
N,N-dιmethyl-(2,4.6-tπmethylanιlιnιum) tetrakιs-(2,3,4,6-tetrafluorophenyl)borate
Dialkyl ammonium salts such as dι-(ι-propy])ammonιum tetrakιs(pentafluorophenyl)borate, and dicyclohexylammonium tetrakιs(pentafluorophenyl)borate
Tπ-substituted phosphonium salts such as triphenylphosphonium tetrakιs(pentafluorophenyl)borate, tπ(o-tolyl)phosphonιum tetrakιs(pentafluorophenyl)borate, and tπ(2 6-dιmethylphenyl)phosphonιum tetrakιs(pentafluorophenyl)borate Preferred are tetrakιs(pentafluorophenyl)borate salts of long chain alkyl mono- and disubstituted ammonium complexes, especially C 14-C20 alkyl ammonium complexes, especially methyldι(octadecyl)ammonιum tetrakιs(pentafluorophenyl)borate and methyldι(tetradecyl)ammonιum tetrakιs(pentafluorophenyl)borate
An especially preferred group of activating cocatalysts is tπs(pentafluorophenyl)borane, N-R3.N-R4 anilinium tetrakιs(pentafluorophenyI)borate where R3 and R4 independently each occurrence are substituted or unsubstituted saturated hydrocarbyl groups having from 1 to 8 carbon atoms, (R ιR2NHCH3)+ (C6H4OH)B(C6F5)3 , or (R 1 R2NHCH3)+ B(C6F5)4 , where R \ and R2 independently each occurrence are substituted or unsubstituted saturated hydrocarbyl groups having from 12 to 30 carbon atoms
Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula
Figure imgf000070_0001
wherein:
Oxe+ is a cationic oxidizing agent having a charge of e+, e is an integer from 1 to 3, and A0"- and d are as previously defined
Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl- substituted ferrocenium, Ag+' or Pb+2 Preferred embodiments of A^" are those anions previously defined with respect to the Bronsted acid containing activating cocatalysts, especially tetrakιs(pentafluorophenyl)borate. Another suitable ion forming, activating cocatalyst comprises a compound which is a salt of a carbenium ion and a noncoordinating, compatible anion represented by the formula.
©+ A-
wherein
©+ is a C ] _20 carbenium ion, and
A" is as previously defined A preferred carbenium ion is the tπtyl cation, i.e triphenyl methy hum
A further suitable ion forming, activating cocatalyst comprises a compound which is a salt of a silylium ion and a noncoordinating, compatible anion represented by the formula
R3Sι(X')q+A-
wherein
R is C ] _ ιo hydrocarbyl, and X', q and A" aie as previously defined.
Preferred silylium salt activating cocatalysts are tπmethylsilylium tetrakispentafluorophenylborate, tπethylsilylium tetrakispentafluorophenylborate and ether substituted adducts thereof. Silylium salts have been previously geneπcally disclosed in J Chem Soc Chem Comm., 1993, 383-384, as well as Lambert, J B , et al , Organometallics, 1994, 13, 2430-2443 The use of the above silylium salts as activating cocatalysts for addition polymerization catalysts is claimed in United States Patent Application entitled, "Silylium Cationic Polymerization Activators For Metallocene Complexes", filed in the names of David Neithamer, David Devore, Robert LaPointe and Robert Mussell on September 12, 1994
Certain complexes of alcohols, mercaptans. silanols, and oximes with tris(pentafluorophenyl)borane are also effective catalyst activators and may be used according to the present invention. Such cocatalysts are disclosed in U S 5.296 433, the teachings of which are herein incorporated by reference
The technique of bulk electrolysis involves the electrochemical oxidation of the metal complex under electrolysis conditions in the presence of a supporting electrolyte comprising a noncoordinating, inert anion. In the technique, solvents, supporting electrolytes and electrolytic potentials for the electrolysis are used such that electrolysis byproducts that would render the metal complex catalytically inactive are not substantially formed during the reaction More particularly, suitable solvents are materials that are liquids under the conditions of the electrolysis (generally temperatures from 0 to 100°C), capable of dissolving the supporting electrolyte, and inert "Inert solvents" are those that are not reduced or oxidized under the reaction conditions employed for the electrolysis It is generally possible in view of the desired electrolysis reaction to choose a solvent and a supporting electrolyte that are unaffected by the electrical potential used for the desired electrolysis Preferred solvents include difluorobenzene (all isomers), dimethoxyethane (DME), and mixtures thereof
The electrolysis may be conducted in a standard electrolytic cell containing an anode and cathode (also referred to as the working electrode and counter electrode respectively) Suitable materials of construction for the cell are glass, plastic, ceramic and glass coated metal The electrodes are prepared from inert conductive materials, by which are meant conductive materials that are unaffected by the reaction mixture or reaction conditions Platinum or palladium are preferred inert conductive materials Normally an ion permeable membrane such as a fine glass frit separates the cell into separate compartments, the working electrode compartment and counter electrode compartment The working electrode is immersed in a reaction medium comprising the metal complex to be activated, solvent, supporting electrolyte, and any other materials desired for moderating the electrolysis or stabilizing the resulting complex The counter electrode is immersed in a mixture of the solvent and supporting electrolyte The desired voltage may be determined by theoretical calculations or experimentally by sweeping the cell using a reference electrode such as a silver electrode immersed in the cell electrolyte The background cell current, the current draw in the absence of the desired electrolysis, is also determined. The electrolysis is completed when the current drops from the desired level to the background level. In this manner, complete conversion of the initial metal complex can be easily detected.
Suitable supporting electrolytes are salts comprising a cation and a compatible, noncoordinating anion, A- Preferred supporting electrolytes are salts corresponding to the formula G+A ; wherein.
G+ is a cation which is nonreactive towards the starting and resulting complex, and
A" is as previously defined.
Examples of cations, G+, include tetrahydrocarbyl substituted ammonium or phosphonium cations having up to 40 nonhydrogen atoms. Preferred cations are the tetra(n-butylammonιum)- and tetraethylammonium- cations
During activation of the complexes of the present invention by bulk electrolysis the cation of the supporting electrolyte passes to the counter electrode and A" migrates to the working electrode to become the anion of the resulting oxidized product. Either the solvent or the cation of the supporting electrolyte is reduced at the counter electrode in equal molar quantity with the amount of oxidized metal complex formed at the working electrode. Preferred supporting electrolytes are tetrahydrocarbylammonium salts of tetrakιs(perfluoroaryl) borates having from 1 to 10 carbons in each hydrocarbyl or perfluoroaryl group, especially tetra(n- butylammonιum)tetrakis(pentafluorophenyl) borate.
A further recently discovered electrochemical technique for generation of activating cocatalysts is the electrolysis of a disilane compound in the presence of a source of a noncoordinating compatible anion. This technique is more fully disclosed and claimed in the previously mentioned United States Patent application entitled, "Silylium Cationic Polymerization Activators For Metallocene Complexes", filed on September 12, 1994. The foregoing electrochemical activating technique and activating cocatalysts may also be used in combination An especially preferred combination is a mixture of a tπ(hydrocarbyl)alumιnum or tπ(hydrocarbyl)borane compound having from 1 to 4 carbons in each hydrocarbyl group with an oligomeric or polymeric alumoxane compound
The molar ratio of catalyst/cocatalyst employed preferably ranges from 1 10,000 to 100 1 , more preferably from 1 -5000 to 10 1 , most preferably from 1 1000 to 1 1 Alumoxane, when used by itself as an activating cocatalyst, is employed in large quantity, generally at least 100 times the quantity of metal complex on a molar basis Tπs(pentafluorophenyl)borane, where used as an activating cocatalyst, is employed in a molar ratio to the metal complex of form 0 5 1 to 10 1 , more preferably from 1 I to 6' 1 , most preferably from 1 1 to 5 1 The remaining activating cocatalysts are generally employed in approximately equimolar quantity with the metal complex
The process may be used to polymerize ethylenically unsaturated monomers having from 2 to 20 carbon atoms either alone or in combination Preferred monomers include monoviny dene aromatic monomers, especially styrene, 4-vιnylcyclohexene, vinylcyclohexane, norbornadiene and C2- ] θ aliphatic α-olefins, especially ethylene, propylene, isobutylene, 1 -butene, 1 -pentene, 1 -hexene, 3-methyl- l-pentene, 4-methyl- 1-pentene, 1 -heptene, and 1-octene, C4.40 dienes, and mixtures thereof Most preferred monomers are ethylene, propylene, 1 -butene, 1 -hexene, 1 -octene nd mixtures of ethylene, propylene and a nonconjugated diene, especially ethylidenenorbomene.
In geneial, the polymerization may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that is, temperatures from 0-250°C, preferably 30 to 200°C and pressures from atmospheric to 10,000 atmospheres Suspension, solution, slurry, gas phase, bulk, solid state powder polymerization or other process condition may be employed if desired A support, especially silica, alumina, or a polymer (especially poly(tetrafluoroethylene) or a polyolefin) may be employed, and desirably is employed when the catalysts are used in a gas phase or slurry polymerization process. The support is preferably employed in an amount to provide a weight ratio of catalyst (based on metal):support from 1 : 100,000 to 1.10, more preferably from 1 :50,000 to 1 :20, and most preferably from 1 - 10,000 to 1 :30. One such polymerization process comprises contacting, optionally in a solvent, one or more α-olefins with a catalyst according to the present invention, in one or more continuous stirred tank or tubular reactors, connected in series or parallel, or in the absence of solvent, optionally in a fluidized bed gas phase reactor, and recovering the resulting polymer. Condensed monomer or solvent may be added to the gas phase reactor as is well known in the art.
In most polymerization reactions the molar ratio of catalyst:polymeπzable compounds employed is from 10~ ' -: 1 to 10" ' : 1 , more preferably from l θX l to 10"5: 1.
Suitable solvents for polymerization are inert liquids. Examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyciohexane. cycloheptane, methylcyclohexane, mcthylcycloheptane, and mixtures thereof; perfluoπnated hydrocarbons such as perfluoπnated C4_ J O alkanes, and the like and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, xylene, ethylbenzene and the like. Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, butadiene, 1 - butene, cyclopentene, 1 -hexene, 1 -heptene, 4-vιnylcyclohexene, vinylcyclohexane, 3- methyl- 1 -pentene, 4-methyl-l-pentene, 1 ,4-hexadιene, 1 -octene, 1 -decene, styrene, divinylbenzene, allylbenzene, vinyltoluene (including all isomers alone or in admixture), and the like. Mixtures of the foregoing are also suitable.
The catalyst systems may be utilized in combination with at least one additional homogeneous or heterogeneous polymerization catalyst in separate reactors connected in series or in parallel to prepare polymer blends having desirable properties. An example of such a process is disclosed in WO 94/00500, equivalent to U S Serial Number 07/904,770, as well as U.S Serial Number 08/10958. filed January 29. 1993. the teachings oi which are hereby incorporated by reference herein
Utilizing the catalyst systems of the present invention copolymers having high comonomer incorporation and correspondingly low density, yet having a low melt index may be readily prepared That is. high molecular weight polymers are readily attained by use of the present catalysts even at elevated reactor temperatures This result is highly desirable because the molecular weight of α-olefin copolymers can be readily reduced by the use of hydrogen or similar chain transfer agent, however increasing the molecular weight of α-olefin copolymers is usually only attainable by reducing the polymerization temperature of the reactor Disadvantageously, operation of a polymerization reactor at reduced temperatures significantly increases the cost of operation since heat must be iemoved from the reactor to maintain the reduced leaction temperature, while at the same time heat must be added to the reactor effluent to vaporize the solvent In addition, productivity is increased due to improved polymer solubility, decreased solution viscosity, and a higher polymer concentration Utilizing the present catalysts, α-olefin homopolymcrs and copolymers having densities from
0 85 g/cm^ to 0 96 g/cπX, and melt flow rates from 0 001 to 10 0 dg/ in are readily attained in a high temperature process
The catalyst systems of the present invention are particularly advantageous for the production of ethylene homopolymers and ethylene/α-olefin copolymers having high levels of long chain branching The use of the catalyst systems of the present invention in continuous polymerization processes, especially continuous, solution polymerization processes, allows for elevated reactor temperatures which favor the formation of vinyl terminated polymer chains that may be incorporated into a growing polymer, thereby giving a long chain branch The use of the present catalysts system advantageously allows for the economical production of ethylene/α-olefin copolymers having processabi ty similar to high pressure, free radical produced low density polyethylene In another aspect of the processes of this invention, a preferred process is a high temperature solution polymerization process for the polymerization of oletins comprising contacting one or more C2-20 ot-olefins under polymerization conditions with a catalyst system of this invention at a temperature from about 100°C to about 250°C More preferred as a temperature range for this process is a temperature from about 120°C to about 200°C, and even more preferred is temperature from about 150°C to about 200°C
The present catalyst systems may be advantageously employed to prepare olefin polymers having improved processing properties by polymerizing ethylene alone or ethylene/α-olefin mixtures with low levels of a "H" branch inducing diene, such as norbornadiene, 1 ,7-octadιene, or 1 ,9-decadιene The unique combination of elevated reactor temperatures, high molecular weight (or low melt indices) at high reactor temperatures and high comonomer reactivity advantageously allows for the economical production of polymers having excellent physical properties and processability Preferably such polymers comprise a C3_20 c -olefin. including ethylene, and a "H"-branchιng comonomer Preferably, such polymers are produced in a solution piocess. most preferably a continuous solution process Alternatively such polymers may be produced in a gas phase process or a slurry process
As previously mentioned, the present catalyst system is particularly useful in the preparation of EP and EPDM copolymers in high yield and productivity The process employed may be either a solution or slurry process both of which are previously known in the art Kaminsky. J Poly Sci . Vol 23, pp 2151 -64 ( 1985) repoπed the use of a soluble bιs(cyclopentadιenyl) zirconium dimethyl-alumoxane catalyst system for solution polymerization of EP and EPDM elastomers U S 5,229,478 disclosed a slurry polymerization process utilizing similar bιs(cyclopentadιenyl) zirconium based catalyst systems
In general terms, it is desirable to produce such EP and EPDM elastomers under conditions of increased reactivity of the diene monomer component The reason for this was explained in the above-identified '478 patent in the following manner, which still remains true despite the advances attained in such reference A major factor affecting production costs and hence the utility of an EPDM is the diene monomer cost. The diene is a more expensive monomer material than ethylene or propylene. Further, the reactivity of diene monomers with previously known metallocene catalysts is lower than that of ethylene and propylene. Consequently, to achieve the requisite degree of diene incorporation to produce an EPDM with an acceptably fast cure rate, it has been necessary to use a diene monomer concentration which, expressed as a percentage of the total concentration of monomers present, is in substantial excess compared to the percentage of diene desired to be incorporated into the final EPDM product Since substantial amounts of unreacted diene monomer must be recovered from the polymerization reactor effluent for recycle the cost of production is increased unnecessarily
Further adding to the cost of producing an EPDM is the tact that, generally, the exposure of an olefin polymerization catalyst to a diene, especially the high concentrations of diene monomer required to produce the requisite level of diene incorporation in the final EPDM product, often reduces the rate or activity at which the catalyst will cause polymerization of ethylene and propylene monomers to proceed Correspondingly, lower throughputs and longer reaction times have been required, compared to the production of an ethylene-propylene copolymer elastomer or other α- olefin copolymer elastomer
The present catalyst system advantageously allows for increased diene reactivity thereby preparing EPDM polymers in high yield and productivity Additionally, the catalyst system of the present invention achieves the economical production of EPDM polymers with diene contents of up to 20 weight percent or higher, which polymers possess highly desirable fast cure rates
The nonconjugated diene monomer can be a straight chain, branched chain or cyclic hydrocarbon diene having from about 6 to about 15 carbon atoms. Examples of suitable nonconjugated dienes are straight chain acyclic dienes such as 1 ,4-hexadιene and 1 ,6-octadιene, branched chain acyclic dienes such as 5-methyl-l ,4-hexadιene, 3,7-dιmethyl- l ,6-octadιene, 3,7-dιmethyl- l ,7-octadιene and mixed isomers ol dihydromyπcene and dihydrooc ene, single ring alicyclic dienes such as 1 ,3-cyclopentadιene, 1 ,4-cyclohexadιene, 1 ,5-cyclooctadιene and 1 ,5-cyclododecadιene and multi-ring alicyclic fused and bridged ring dienes such as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bιcyclo-(2,2, l )-hepta-2. 5-dιene, alkenyl, alkylidene, cycloalkenyl and cycloalky dene norbornenes such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-ιsopropylιdene-2- norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cycIohexyhdene-2-norbornene, 5- vιnyl-2-norbornene and norbornadiene
Of the dienes typically used to prepare EPDMs, the particularly preferred dienes aie 1 ,4-hexadιene (HD), 5-ethylιdene-2-norbornene (ENB), 5-vιnylιdene-2- noibornene (VNB), 5-methylene-2-norbornene (MNB ). and dicyclopentadiene (DCPD) The especially preferred dienes are 5-ethyhdene-2-norbornene (ENB) and 1 ,4-hexadιene (HD)
The preferred EPDM elastomers may contain about 20 up to about 90 weight percent ethylene, more preferably about 30 to 85 weight percent ethylene, most preferably about 35 to about 80 weight percent ethylene
The alpha-olefins suitable for use in the preparation of elastomers with ethylene and dienes are preferably C3. ] g alpha-olefins Illustrative non-limiting examples of such alpha-olefins are propylene, 1 -butene 1 -pentene, 1 -hexene, 4- methyl- 1 -pentene, 1 -heptene, 1-octene, 1 -decene, and 1 -dodecene The alpha-olefin is generally incorporated into the EPDM polymer at about 10 to about 80 weight percent, more preferably at about 20 to about 65 weight percent The nonconjugated dienes are generally incorporated into the EPDM at about 0 5 to about 20 weight percent, more, preferably at about 1 to about 15 weight percent, and most preferably at 3 to about 12 weight percent If desired, more than one diene may be incorporated simultaneously, for example HD and ENB, with total diene incorporation within the limits specified above The catalyst system may be prepared as a homogeneous catalyst by addition of the requisite components to a solvent in which polymerization will be carried out by solution polymerization procedures The catalyst system may also be prepared and employed as a heterogeneous catalyst by adsorbing the requisite components on a catalyst support material such as silica gel, alumina or other suitable inorganic support material When prepared in heterogeneous or supported form, it is preferred to use silica as the support material Inorganic support materials, such as, for example silica, may be treated with aluminum alkyls or other chemical pacification agents to reduce surface hydroxyl content of the support The heterogeneous form of the catalyst system may be employed in a gas phase or slurry polymerization As a practical limitation, slurry polymerization takes place in liquid diluents under conditions in which the polymer product is substantially insoluble Preferably, the diluent for slurry polymerization is one or more hydrocarbons with less than 5 carbon atoms If desired, saturated hydrocarbons such as ethane, propane or butane may be used in whole or part as the diluent Likewise the α-olcfin monomer or a mixture of diffeient α-olefin monomers may be used in whole or part as the diiuent Most preferably the diluent comprises in at least major part the α-olef in monomer or monomers to be polymerized
The catalyst system of this invention may comprise an aluminum organometalhc component which comprises an alumoxane, an aluminum alkyl or a combination thereof This component may be present in a nonactivating amount and function primarily as a scavenger, or it may interact with the cocatalyst component to enhance the activity of the catalyst component, or it may do both
It is understood with suitable functionality on the catalyst or cocatalyst of the catalyst system can be covalently or lonically attached to the support material of the support component, which comprises a support material which is a polymer, an inorganic oxide, a metal halide, or a mixture thereof
Preferred supports for use in the present invention include highly porous silicas aluminas, aluminosilicates, and mixtures thereof The most preferred support material is silica The support material may be in granular, agglomerated, pelletized, or any other physical form. Suitable materials include, but are not limited to, silicas available from Grace Davison (division of W.R. Grace & Co ) under the designations SD 3216 30, Davison Syloid 245, Davison 948 and Davison 952, and from Crossfield under the designation ES70, and from Degussa AG under the designation Aerosil 812, and aluminas available from Akzo Chemicals Inc. under the designation Ketzen Grade B
Supports suitable for the present invention preferably have a surface area as determined by nitrogen porosimetry using the B E T. method from 10 to about 1000 n g, and preferably from about 100 to 600 π g. The pore volume of the support, as determined by nitrogen adsorption, advantageously is between 0 1 and 3 cm^/g, preferably from about 0 2 to 2 cπX/g The average particle size depends upon the process employed, but typically is from 0 5 to 500 μm, preferably from 1 to 100 μm.
Both silica and alumina are known to inherently possess small quantities of hydroxyl functionality. When used as a support herein, these materials are preferably subjected to a heat treatment and/or chemical treatment to reduce the hydroxyl content thereof Typical heat treatments are carried out at a temperature from 30°C to 1000°C (preferably 250°C to 800°C for 5 hours or greater) for a duration of 10 minutes to 50 hours in an inert atmosphere or under reduced pressure. Typical chemical treatments include contacting with Lewis acid alkylating agents such as tπhydrocarbyl aluminum compounds, tπhydrocarbylchlorosilane compounds, tπhydrocarbylalkoxysilane compounds or similar agents. Residual hydroxyl groups are then removed via chemical treatment
The support may be functionahzed with a silane or chlorosilane functionalizing agent to attach thereto pendant silane -(Sι-R)=, or chlorosilane -(Sι-Cl)= functionality, wherein R is a C j. io hydrocarbyl group. Suitable functionalizing agents are compounds that react with surface hydroxyl groups of the support or react with the silicon or aluminum of the matrix. Examples of suitable functionalizing agents include phenylsilane, hexamethyldisilazane diphenylsilane, methylphenylsilane. dimethylsilane, diethylsilane, dichlorosilane, and dichlorodimethylsilane. Techniques for forming such functionahzed silica or alumina compounds were previously disclosed in U S Patents 3,687,920 and 3.879,368, the teachings of which arc herein incorporated by reference
The support may also be treated with an aluminum component selected from an alumoxane or an aluminum compound of the formula AIR ' x R-y , wherein R ' independently each occurrence is hydride or R, R- is hydride, R or OR, x' is 2 or 3, y' is 0 or 1 and the sum of x' and y' is 3 Examples of suitable R ' and R^ groups include methyl, methoxy, ethyl, ethoxy, propyl (all isomers), propoxy (all isomers), butyl (all isomers), butoxy (all isomers), phenyl, phenoxy, benzyl, and benzyloxy Preferably, the aluminum component is selected from the group consisting of aluminoxanes and tπ(C i .4 hydrocarbyOaluminum compounds Most preferred aluminum components are aluminoxanes. tπmethylaluminum, tπethylaluminum, tπ-isobutylaluminum. and mixtures thereof
Alumoxanes (also referred to as aluminoxanes) are oligomeric or polymeric aluminum oxy compounds containing chains of alternating aluminum and oxygen atoms, whereby the aluminum carries a substituent, preferably an alkyl group The structure of alumoxane is believed to be represented by the following general formulae (-Al(R)-O)m' , for a cyclic alumoxane, and R2Al-O(-Al(R)-O)rn'-AlR2, for a linear compound, wherein R is as previously defined, and m' is an integer ranging from I to about 50, preferably at least about 4 Alumoxanes are typically the reaction products of water and an aluminum alkyl, which in addition to an alkyl group may contain halide or alkoxide groups. Reacting several different aluminum alkyl compounds, such as for example tπmethyl aluminum and tπ-isobutyl aluminum, with water yields so-called modified or mixed alumoxanes. Preferred alumoxanes are methylalumoxane and methylalumoxane modified with minor amounts of C2-4 alkyl groups, especially isobutyl Alumoxanes generally contain minor to substantial amounts of starting aluminum alkyl compound
Particular techniques for the preparation of alumoxane type compounds by contacting an aluminum alkyl compound with an inorganic salt containing water of crystallization are disclosed in U.S 4,542, 1 19. In a particular preferred embodiment an aluminum alkyl compound is contacted with a regeneratable water-containing substance such as hydrated alumina, silica or other substance This is disclosed in EP- A-338,044. Thus the alumoxane may be incorporated into the support by reaction of a hydrated alumina or silica material, which has optionally been functionalized with silane, siloxane, hydrocarbyloxysilane, or chlorosilane groups, with a tn (C μjo alkyl) aluminum compound according to known techniques. For the teachings contained therein the foregoing patents and publications, or there corresponding equivalent United States applications, are hereby incorporated by reference
The treatment of the support material in order to also include optional alumoxane or tπalkylaluminum loadings involves contacting the same before, after or simultaneously with addition of the complex or activated catalyst hereunder with the alumoxane or trialkyialummum compound, especially tπethylaluminum or tmsobutylaluminum. Optionally the mixture can also be heated under an men atmosphere for a period and at a temperature sufficient to fix the alumoxane, trialkyialummum compound, complex or catalyst system to the support. Optionally, the treated support component containing alumoxane or the trialkyialummum compound may be subjected to one or more wash steps to remove alumoxane or trialkyialummum not fixed to the support.
Besides contacting the support with alumoxane the alumoxane may be generated in situ by contacting an unhydrolyzed silica or alumina or a moistened silica or alumina with a tπalkyl aluminum compound optionally in the presence of an inert diluent. Such a process is well known in the art, having been disclosed in EP-A- 250,600; U S -A-4,912.075. and U.S -A-5,008,228, the teachings of which, or of the corresponding U S application, are hereby incorporated by reference Suitable aliphatic hydrocarbon diluents include pentane, isopentane, hexane, heptane, octane, isooctane, nonane. isononane, decane, cyciohexane, methylcyclohexane and combinations of two or more of such diluents Suitable aromatic hydrocarbon diluents are benzene, toluene, xylene, and other alkyl or halogen substituted aromatic compounds. Most preferably, the diluent is an aromatic hydrocarbon, especially toluene After preparation in the foregoing manner the residual hydroxyl content thereof is desirably reduced to a level less than 1 0 meq of OH per gram of support by any of the previously disclosed techniques
The cocatalysts of the invention may also be used in combination with a tπ(hydrocarbyl)alumιnum compound having from 1 to 10 carbons in each hydrocarbyl group, an oiigomeπc or polymeric alumoxane compound, a dι(hydrocarbyl)(hydrocarbyloxy)alumιnum compound having from 1 to 10 carbons in each hydrocarbyl or hydrocarbyloxy group, or a mixture of the foregoing compounds, if desired These aluminum compounds are usefully employed for their beneficial ability to scavenge impurities such as oxygen, water, and aldehydes from the polymerization mixture Preferred aluminum compounds include C2-6 tnalkyl aluminum compounds, especially those wherein the alkyl groups are ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl, or isopentyl, and methylalumoxane, modified methylalumoxane and dusobutylalumoxane The molar ratio of aluminum compound to metal complex is preferably from 1 10,000 to 1000 1 , more preferably from 1 5000 to 100 1. most preferably from 1 100 to 100 1
Solution polymerization takes place under conditions in which the diluent acts as a solvent for the respective components of the reaction, particularly the EP or EPDM polymer Preferred solvents include mineral oils and the various hydrocarbons which are liquid at reaction temperatures Illustrative examples of useful solvents include alkanes such as pentane, isopentane, hexane, heptane, octane and nonane, as well as mixtures of alkanes including kerosene and Isopar E™, available from Exxon Chemicals Inc , cycloaikanes such as cyclopentane and cyciohexane, and aromatics such as benzene, toluene, xylenes, ethylbenzene and diethylbenzene
At all times, the individual ingredients as well as the recovered catalyst components must be protected from oxygen and moisture Therefore, the catalyst components and catalysts must be prepared and recovered in an oxygen and moisture free atmosphere Preferably, therefore, the reactions are performed in the presence of a dry, inert gas such as, for example, nitrogen Ethylene is added to the reaction vessel in an amount to maintain a differential pressure in excess of the combined vapor pressure of the α-olefin and diene monomers. The ethylene content of the polymer is determined by the ratio of ethylene differential pressure to the total reactor pressure. Generally the polymerization process is carried out with a differential pressure of ethylene of from about 10 to about 1000 psi (70 to 7000 kPa), most preferably from about 40 to about 400 psi (30 to 300 kPa) The polymerization is generally conducted at a temperature of from 25 to 200°C, preferably from 75 to 170°C, and most preferably from greater than 95 to 140°C.
The polymerization may be carried out as a batchwise or a continuous polymerization process. A continuous process is preferred, in which event catalyst, ethylene, α-olefin. and optionally solvent and diene are continuously supplied to the reaction zone and polymer product continuously removed therefrom Within the scope of the terms "continuous" and "continuously" as used in this context are those processes in which there are intermittent additions of reactants and removal of products at small regular intervals, so that, over time, the overall process is continuous.
Without limiting in any way the scope of the invention, one means for carrying out such a polymerization process is as follows: In a stirred-tank reactor propylene monomer is introduced continuously together with solvent, diene monomer and ethylene monomer The reactor contains a liquid phase composed substantially of ethylene, propylene and diene monomers together with any solvent or additional diluent If desired, a small amount of a "H"-branch inducing diene such as norbornadiene, 1 ,7-octadιene or 1 ,9-decadιene may also be added. Catalyst and cocatalyst are continuously introduced in the reactor liquid phase. The reactor temperature and pressure may be controlled by adjusting the solvent/monomer ratio, the catalyst addition rate, as well as by cooling or heating coils, jackets or both. The polymerization rate is controlled by the rate of catalyst addition. The ethylene content of the polymer product is determined by the ratio of ethylene to propylene in the reactor, which is controlled by manipulating the respective feed rates of these components to the reactor. The polymer product molecular weight is controlled. optionally, by controlling other polymerization variables such as the temperature. monomer concentration, or by a stream of hydrogen introduced to the reactor, as is well known in the art. The reactor effluent is contacted with a catalyst kill agent such as water The polymer solution is optionally heated, and the polymer product is recovered by flashing off gaseous ethylene and propylene as well as residual solvent or diluent at reduced pressure, and, if necessary, conducting further devoiatilization in equipment such as a devolati zing extruder In a continuous process the mean residence time of the catalyst and polymer in the reactor generally is from about 5 minutes to 8 hours, and preferably from 10 minutes to 6 hours
In a preferred manner of operation, the polymerization is conducted in a continuous solution polymerization system comprising two reactors connected in series or parallel In one reactor a relatively high molecular weight product (Mw from 300.000 to 600,000, more preferably 400.000 to 500,000) is formed while in the second reactor a product of a relatively low molecular weight (Mw 50,000 to 300,000) is formed The final product is a blend of the two reactor effluents which are combined prior to devoiatilization to result in a uniform blend of the two polymer products Such a dual reactor process allows tor the preparation of products having improved properties In a preferred embodiment the reactors are connected in series, that is effluent from the first reactor is charged to the second reactor and fresh monomer, solvent and hydrogen i added to the second reactor Reactor conditions are adjusted such that the weight ratio of polymer produced in the first reactor to that produced in the second reactor is from 20 80 to 80.20 In addition the temperature of the second reactor is controlled to produce the lower molecular weight product This system beneficially allow for production of EPDM products having a large range ol Mooney viscosities, as well as excellent strength and processability Preferably the Mooney viscosity (ASTM D 1646-94, ML 1 +4 @ 125°C) of the resulting product is adjusted to fall in the range from 1 to 200, preferably from 5 to 150 and most preferably from 10 to 1 10
The process of the present invention can be employed to advantage in the gas phase copolymeπzation of olefins. Gas phase processes for the polymerization of olefins, especially the homopolymerization and copolymeπzation of ethylene and propylene, and the copolymerization of ethylene with higher α-olefins such as, for example, 1 -butene, 1 -hexene, 4-methyl- l -pentene are well known in the art. Such processes are used commercially on a large scale for the manufacture of high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE) and polypropylene.
The gas phase process employed can be, for example, of the type which employs a mechanically stirred bed or a gas fluidized bed as the polymerization reaction zone. Preferred is the process wherein the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported or suspended above a perforated plate, the tluidization grid, by a flow of fluidization gas.
The gas employed to fluidize the bed comprises the monomer or monomers to be polymerized, and also serves as a heat exchange medium to remove the heat of reaction from the bed. The hot gases emerge from the top of the reactor, normally via a tranquilization zone, also known as a velocity reduction zone, having a wider diameter than the fluidized bed and wherein fine particles entrained in the gas stream have an opportunity to gravitate back into the bed. It can also be advantageous to use a cyclone to remove ultra-fine particles from the hot gas stream. The gas is then normally recycled to the bed by means of a blower or compressor and one or more heat exchangers to strip the gas of the heat of polymerization.
A preferred method of cooling of the bed, in addition to the cooling provided by the cooled recycle gas, is to feed a volatile liquid to the bed to provide an evaporative cooling effect, often referred to as operation in the condensing mode. The volatile liquid employed in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon having about 3 to about 8, preferably 4 to 6. carbon atoms. In the case that the monomer or comonomer itself is a volatile liquid, or can be condensed to provide such a liquid, this can suitably be fed to the bed to provide an evaporative cooling effect. Examples of olefin monomers which can be employed in this manner are olefins containing about three to about eight, preferably three to six carbon atoms. The volatile liquid evaporates in the hot fluidized bed to form gas which mixes with the fluidizing gas. If the volatile liquid is a monomer or comonomer, it will undergo some polymerization in the bed. The evaporated liquid then emerges from the reactor as part of the hot recycle gas, and enters the compression/heat exchange part of the recycle loop. The recycle gas is cooled in the heat exchanger and, if the temperature to which the gas is cooled is below the dew point, liquid will precipitate from the gas. This liquid is desirably recycled continuously to the fluidized bed. It is possible to recycle the precipitated liquid to the bed as liquid droplets carried in the recycle gas stream. This type of process is described, for example in EP 89691 ; U.S. 4,543,399; WO 94/25495 and U.S. 5.352,749, which are hereby incorporated by reference. A particularly preferred method of recycling the liquid to the bed is to separate the liquid from the recycle gas stream and to reinject this liquid directly into the bed, preferably using a method which generates fine droplets of the liquid within the bed. This type of process is described in BP Chemicals' WO 94/28032, which is hereby incorporated by reference.
The polymerization reaction occurring in the gas fluidized bed is catalyzed by the continuous or semi-continuous addition of catalyst. Such catalyst can be supported on an inorganic or organic support material as described above. The catalyst can also be subjected to a prepolymerization step, for example, by polymerizing a small quantity of olefin monomer in a liquid inert diluent, to provide a catalyst composite comprising catalyst particles embedded in olefin polymer particles.
The polymer is produced directly in the fluidized bed by catalyzed copolymerization of the monomer and one or more comonomers on the fluidized particles of catalyst, supported catalyst or prepolymer within the bed. Start-up of the polymerization reaction is achieved using a bed of preformed polymer particles, which are preferably similar to the target polyolefin, and conditioning the bed by drying with inert gas or nitrogen prior to introducing the catalyst, the monomers and any other gases which it is desired to have in the recycle gas stream, such as a diluent gas. hydrogen chain transfer agent, or an inert condensable gas when operating in gas phase condensing mode. The produced polymer is discharged continuously or discontinuously from the fluidized bed as desired.
The gas phase processes suitable for the practice of this invention are preferably continuous processes which provide for the continuous supply of reactants to the reaction zone of the reactor and the removal of products from the reaction zone of the reactor, thereby providing a steady-state environment on the macro scale in the reaction zone of the reactor.
Typically, the fluidized bed of the gas phase process is operated at temperatures greater than 50°C, preferably from about 60°C to about 1 10°C, more preferably from about 70°C to about 1 10°C.
Typically the molar ratio of comonomer to monomer used in the polymerization depends upon the desired density for the composition being produced and is about 0 5 or less. Desirably, when producing materials with a density range of from about 0.91 to about 0.93 the comonomer to monomer ratio is less than 0.2, preferably less than 0.05, even more preferably less than 0.02, and may even be less than 0 01 Typically, the ratio of hydrogen to monomer is less than about 0.5, preferably less than 0.2, more preferably less than 0.05, even more preferably iess than 0.02 and may even be less than 0.01.
The above-described ranges of process variables arc appropπate for the gas phase process of this invention and may be suitable for other processes adaptable to the practice of this invention.
A number of patents and patent applications describe gas phase processes which are adaptable for use in the process of this invention, particularly, U.S. Patents 4,588,790; 4,543,399; 5,352,749; 5,436.304; 5,405,922. 5,462,999, 5,461 , 123; 5,453,471 ; 5,032,562; 5,028,670; 5,473,028. 5, 106,804, and EP applications 659.773, 692.500; and PCT Applications WO 94/29032, WO 94/25497, WO 94/25495, WO 94/28032; WO 95/13305; WO 94/26793, and WO 95/07942 all of which are hereby incorporated herein by reference The catalysts, whether or not supported in any of the foregoing methods may be used to polymerize ethylemcally and/or acetylenically unsaturated monomers having from 2 to 100,000 carbon atoms either alone or in combination Preferred monomers include the C2-20 ct-olefins especially ethylene, propylene, isobutylene, 1-butene, 1-pentene, 1 -hexene, 3-methyl-l-pentene, 4-methyl- l -pentene, 1 -octene, 1 -decene, long chain macromolecular α-olefins, and mixtures thereof Other preferred monomers include styrene, C] _4 alkyl substituted styrene, tetrafluoroethylene, vinylbenzocyclobutane, ethylidenenorbomene, 1 ,4-hexadιene, 1 ,7-octadιene, vinylcyclohexane, 4-vιnylcyclohexene, divinylbenzene, and mixtures thereof with ethylene Long chain macromolecular α-olefins are vinyl terminated polymeric remnants formed in situ during continuous solution polymerization reactions Under suitable processing conditions such long chain macromolecular units are readil) polymerized into the polymer product along with ethylene and other short chain olefin monomers to give small quantities of long chain branching in the resulting polymer
The catalysts may also be utilized in combination with at least one additional homogeneous 01 heterogeneous polymerization catalyst in the same or in separate reactors connected in series or in parallel to prepare polymer blends having desirable properties An example of such a process is disclosed in WO 94/00500, equivalent to U S Serial Number 07/904,770, as well as U S Serial Number 08/10958, filed January 29, 1993, the teachings or which are hereby incorporated by reference herein
For the preferred polyolefin polymer compositions of this invention, which may be produced by the polymerization processes of this invention using the catalyst systems of this invention, the long chain branch is longer than the short chain branch that results from the incorporation of one or more α-olefin comonomers into the polymer backbone The empirical effect of the presence of long chain branching in the copolymers of this invention is manifested as enhanced rheological properties which are indicated by higher flow activation energies, and greater L1/I2 than expected from the other structural properties of the compositions Further, highly preferred polyolefin copolymer compositions of this invention have reverse molecular architecture, that is, there is a molecular weight maximum which occurs in that 50 percent by weight of the composition which has the highest weight percent comonomer content. Even more preferred are polyolefin copolymer compositions which also have long chain branches along the polymer backbone, especially when produced with a catalyst system of this invention having a single metallocene complex of this invention in a single reactor in a process for the polymerization of an α-olefin monomer with one or more olefin comonomers, more especially when the process is a continuous process
Measurement of comonomer content vs log molecular weight by GPC/FTIR
The comonomer content as a function of molecular weight can be measured by coupling a Fourier transform infrared spectrometer (FTIR) to a Waters 150°C Gel Permeation Chromatograph (GPC) The setting up, calibration and operation of this system together with the method for data treatment has been described previously (L J Rose et al, "Characterisation of Polyethylene Copolymers by Coupled GPC/FTIR" in "Characterisation of Copolymers", Rapra Technology, Shawbury UK, 1995, ISBN 1 - 85957-048-86 ) In order to characterize the degree to which the comonomer is concentrated in the high molecular weight part of the polymer, the GPC FTIR is used to calculate a parameter named comonomer partition factor, Cpf Mn and M are also determined using standard techniques from the GPC data.
Comonomer Partitioning Factor (GPC-FTIR)
The comonomer partitioning factor Cpf is calculated from GPC/FTIR data It characterizes the ratio of the average comonomer content of the higher molecular weight fractions to the average comonomer content of the lower molecular weight fractions Higher and lower molecular weight are defined as being above or below the median molecular weight respectively, that is, the molecular weight distribution is divided into two parts of equal weight. Cpf is calculated from the following equation ∑ »l ' I r=l
Σ ".
1 = 1
Cpf = , Σ=ι ' ; .where c, is the mole fraction comonomer content and w, is the in "7 7=1 normalized weight fraction as determined by GPC/FTIR for the n FTIR data points above the median molecular weight, c, is the mole fraction comonomer content and w, is the normalized weight fraction as determined by GPC/FTIR for the m FTIR data points below the median molecular weight Only those weight tractions, w, or w, which have associated mole fraction comonomer content values are used to calculate Cp[ For a valid calculation, it is required that n and m arc greater than or equal to 3
FTIR data corresponding to molecular weight fractions below 5 000 are not included in the calculation due to the uncertainties present in such data
For the polyolefin copolymer compositions of this invention, Cpf desirably is equal to or greater than 1 10, more desirably is equal to ot greater than I 15 even more desirably is equal to or greater than 1 20, preferably is equal to or greater than 1 30 more preferably is equal to or greater than 1 40, even more preferably is equal to or greater than 1 50, and still more preferably is equal to or greater than 1 60
ATREF-DV
ATREF-DV has been described in U S Patent No 4,798.081 , which is hereby incorporated by reference, and in "Determination of Short-Chain Branching Distributions of Ethylene copolymers by Automated Analytical Temperature Rising Elution Fractionation" (Auto-ATREF), J of Appl Pol Sci Applied Polymer Symposium 45, 25-37 (1990) ATREF-DV is a dual detector analytical system that is capable of fractionating semi-crystalline polymers like Linear Low Density Polyethylene (LLDPE) as a function of crystallization temperature while simultaneously estimating the molecular weight of the fractions With regard to the fractionation, ATREF-DV is analogous to Temperature Rising Elution Fractionation (TREF) analysis that have been published in the open literature over the past 15 years The primary difference is that this Analytical - TREF (ATREF) technique is done on a small scale and fractions are not actually isolated Instead, a typical liquid chromatographic (LC) mass detector, such as an infrared single frequency detector, is used to quantify the crystallinity distribution as a function of elution temperatuie This distribution can then be transformed to any number of alternative domains such as short branching frequency, comonomer distribution, or possibly density Thus, this transformed distribution can then be interpreted according to some structural variable like comonomer content, although routine use of ATREF for comparisons of various LLDPE's is often done directly in the elution temperature domain
To obtain ATREF-DV data, a commercially available viscometer especially adapted for LC analysis, such as a Viskotek™ is coupled with the IR mass detector Together these two LC detectors can be used to calculate the intrinsic viscosity of the ATREF-DV eluant The viscosity average molecular weight of a given fraction can then be estimated using appropriate Mark Houwink constants, the corresponding intrinsic viscosity, and suitable coefficients to estimate the fractions concentration (dl/g) as it passes through the detectors Thus, a typical ATREF-DV report will provide the weight fraction polymer and viscosity average molecular weight as a function of elution temperature Mp is then calculated using the equation given
Molecular Weight Partitioning Factor
The molecular weight partitioning factor Mpf is calculated from TREF/DV data It characterizes the ratio of the average molecular weight of the fractions with high comonomer content to the average molecular weight of the fractions with low comonomer content Higher and lower comonomer content are defined as being below or above the median elution temperature of the TREF concentration plot respectively, that is, the TREF data is divided into two parts of equal weight. Mpf is calculated from the following equation , where: M, is the viscosity average molecular weight and w, is
Figure imgf000094_0001
the normalized weight fraction as determined by ATREF-DV for the n data points in the fractions below the median elution temperature M, is the viscosity average molecular weight and w, is the normalized weight fraction as determined by ATREF- DV for the m data points in the fractions above the median elution temperature Only those weight fractions, w, or w, which have associated viscosity average molecular weights greater than zero are used to calculate Mpf For a valid calculation, it is required that n and m are greater than or equal to 3
For the polyolefin copolymer compositions of this invention, Mpf desirably is equal lo or greater than 1 15, more desirably is equal to or greater than 1 30. even more desirably is equal to or greater than 1 40, preferably is equal to or greater than I 50, more preferably is equal to or greater than 1 60, even more preferably is equal to or greater than 1 70
Examples
The skilled artisan will appreciate that the invention disclosed herein may be practiced in the absence of any component which has not been specifically disclosed The following examples are provided as further illustration of the invention and are not to be construed as limiting Unless stated to the contrary all parts and percentages are expressed on a weight basis.
General Considerations All experiments involving organometalhc compounds were carried out using drybox techniques Solvents (THF, hexane toluene diethylether) were purified by passing through alumina and Q5 columns C Dg was dried under over Na K alloy and vacuum distilled before use NMR spectra were measured on a
Vanan XL-300 (FT 300 MHz, ' H, 75 MHz, ! 3C) 1 H NMR and 3C ( ! H } NMR spectra are referenced to the residual solvent peaks and are reported in ppm relative to tetramethylsilane. All J values are given in Hz. Mass spectra (El) were obtained on the AutoSpecQFDP. 1 -indanone, «-BuLι, Me2SiCh. NH2-f-Bu, NEt3 and MeMgl were purchased from Aldrich Chemical Co. All compounds were used as received.
N-( l H-2-ιndenyl)-N,N-dιmethylamιne [Acta Chem. Scand., 1973. 27, 4027), l-( lH-2-indenyl)-pyrrohdιne crα Chem. Scand., 1973, 27, 4027), 2-ethoxy- lH- mdene (j. Am. Chem. So.. 1954, 106, 14), and r<?rr-butyl-(lH-2-ιndenyloxy)- dimethylsilane {Organometallics, 1996, 15, 2450) were prepared by literature procedures.
Figure imgf000095_0001
( 1 )
Preparation of N-( 1 H-2-ιndenyl)-N,N-dιmethylamιne, lithium salt, ( 1 ). In the drybox 1 1 .93 g (75.92 mmol) of N-( l H-2-ιndenyl)-N,N-dιmethylamιne was dissolved in mixture of 200 mL of ether and 100 mL of hexane. To this solution 51.51 mL
(82 42 mmol) of /ι-BuLι ( 1.6 M) was added dropwise Upon complete addition of the /ι-BuLι the solution was stirred overnight The resulting off-white precipitate was collected via filtration, washed with 100 mL of ether and dried under reduced pressure to give 10.22 g of product. Yield 83 percent.
Figure imgf000095_0002
(2) Preparation of N2,N2,-dιmethyl- 1 -( 1 -(tert-bυly lamino)- 1 , 1 -dimethylsilyl)- 1 H- 2-ιndenamιne, (2) A solution of N-( 1 H-2-ιndeny l)-N,N-dimethy lamine, lithium salt (2.07 g, 12.53 mmol) in 40 mL of THF was added within 30 minutes to a 30 mL THF solution of N-( rf-butyl)-N-( l-chloro- l .l-dimethylsιlyI)amιne. The reaction mixture was stirred for 7 hours and then the solvent was removed in vacuum. The product was extracted with 30 mL of hexane and the solution was filtered through a medium size glass tπt. Hexane was removed under reduced pressure leaving 3.48 g of product as a white solid Yield 96 percent.
1 H (C6D6) δ -0.01 (s, 3H), 0 1 1 (s, 3H), 1.00 (s, 1 H), 1 09 (s. 9H), 2 43 (s, 6H), 3 40 (s, IH), 5.63 (s, IH), 7.08 (t, IH, 3yH-H = 7 1 Hz), 7.23-7.32 (m, 2H). 7 40 (d, I H, 37H H = 7 4 HZ).
1 3C{ Η }(C6D6) δ -0.75, 0.39, 34 08, 42 44, 45.23, 49.47, 102.42, 1 18 31 , 120.46, 122.63. 125 49. 140.45, 146.08, 161.75.
Figure imgf000096_0001
(3)
Preparation of N2,N2, -dimethyl- 1 -( I -(/err-butylamino)- 1.1 -dimethylsilyl)- 1 H- 2-ιndenamιne, di thium salt, (3). In the drybox 3.48 g ( 12.06 mmol) of N2,N2,- dιmethyl- l -( l -(fer'-butylamιno)- 1 , 1 -dimethylsilyl)- lH-2-ιndenamιne was dissolved in 80 mL of hexane To this solution 18.0 mL (28.8 mmol) of n-BuLi ( 1.6 M) was added dropwise. Upon complete addition of the «-BuLι the solution was stirred overnight.
The resulting precipitate was collected via filtration, washed with 50 mL of hexane and dried under reduced pressure to give 3.40 g of white solid. Yield 94 percent.
Figure imgf000097_0001
(4)
Preparation of dιchloro(N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)- 2-dιmethylamιno- 1 H-inden- 1 -yl)sιlanamιnato-(2-)-N-)-tιtanιum, (4). N2.N2,- Dimethyl- 1 -( 1 -(rerr-butylamino)- 1 , 1 -dimethylsilyl)- 1 H-2-ιndenamιne, dilithium salt (3 40 g, 1 1.3 mmol) dissolved in 30 mL of THF was added within 2 minutes to a suspension of TiCl3(THF)3 (4.19 g, 1 1.3 mmol) in 60 mL of THF. After 1 hour of mixing, PbCh (2.04 g, 7 34 mmol) was added as a solid. The reaction mixture was stirred an additional 1.5 hours. The solvent was removed under reduced pressure. The residue was extracted with 70 mL of toluene and filtered through a medium size glass frit. Toluene was removed under reduced pressure and the residue was triturated with 50 mL of hexane. The brown-red solid was collected by filtration, washed with hexane (2 x 30 mL), then dried under reduced pressure to give 3.22 g of product as a brown- red solid. Yield 70 percent.
Η (C6D6) δ 0 48 (s, 3H), 0.64 (s, 3H), 1.28- 1 5 (br. 6H), 1.38 (s, 9Hl. 3 19
(m, 2H), 3.58 (m, 3H), 5 92 (s, IH), 6.98 (t, IH, 37H-H = 7.5 Hz), 7.09 (t, I H, 3 I-H = 7 5 Hz), 7.52 (d, I H, 37H H = 8.5 Hz), 7 63 (d, IH, 3 H-H = 8 7 Hz).
1 3C{ lH }(CβO6) δ 1.35, 4. 15, 24.35, 26.14, 32.88, 51.62, 61.46, 92.92, 1 1 1 79, 125.08, 128.67. 128 92, 135.42, 151.09.
Figure imgf000098_0001
(5)
Preparation of (N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a.7a-η)-2- dimethylamino- 1 H-inden- 1 -yl)sιlanamιnato-(2-)-N-)-dιmethyl-tιtanιum, (5). In the drybox 0.60 g of dιchloro(N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2- dιmethylamιno- 1 H-mden- l-yl)sιlanamιnato-(2-)-N-)-tιtanιum ( I 48 mmol) was dissolved in 35 mL of Et2θ To this solution 1.00 mL (3.00 mmol) of MeMgl (3 0 M) was added dropwise with stirring over a 5 minute period. The solution changed color from deep brown to green-yellow. After the addition of MeMgl was completed, the solution was stirred for 60 minutes. The Et2θ was removed under reduced pressure and the residue was extracted with hexane (2 x 20 mL), the solution was filtered and the filtrate was evaporated to dryness under reduced pressure to give 0 29 g (53 percent yield) of yellow-green solid.
1 H (C0D6) δ 0 01 (s, 3H), 0.58 (s, 3H), 0.63 (s, 3H), 0.98 (s, 3H), 1.52 (s, 9H). 2 45 (s, 6H), 6 17 (s, I H), 6.88 (t, I H, 37H n = 6 Hz), 7.12 (t, I H, 37H-H = 8 0 Hz), 7.40 (d, 1 H, 3/H H = 8.3 Hz), 7.50 (d, 1 H, 37H-H = 8.32 Hz)
13C{ ^ )(C(,O ) δ 5.55, 6.71 , 34.65, 45.87, 51.00, 57.97, 58.29. 79.96, 95.64, 124.23, 124.96. 125.46, 126.95, 130.3 1 , 131.87, 161.99.
Figure imgf000099_0001
(6)
Preparation of l -( l H-2-ιndenyl)pyrrolιdιne, lithium salt, (6) In the drybox 15 2 g (82.2 mmol) of 2-pyrrohdιno-ιndene was dissolved in a mixture of 150 mL of toluene and 200 mL of ether To this solution 53 84 mL (86.16 mmol) of w-BuLi ( 1.6 M) was added dropwise at room temperature Upon complete addition of the rc-BuLi the solution was stirred overnight The resulting off-white piecipitate was collected via filtration, washed with 70 L of hexane and dried under reduced pressure to give 15.29 g of product Yield 97.5 percent
Figure imgf000099_0002
(7)
Preparation of N-(/er/-butyl)-N-( I . I -dιmethyl-2-(2-tetrahydro- 1 H- 1 -pyrrolyi- l H-1-ιndeny sιly amme, (7) A solution of l -( l H-2-ιndenyl)pyrrolιdιne, lithium salt (5 0 g, 26 15 mmol) in 50 mL of THF was added within 10- 15 minutes to a 50 mL THF solution of N-(rerr-buty l)-N-( 1 -chloro- 1 , 1 -dimethylsily Oamine (4 98 g, 30.07 mmol) The reaction mixture was stirred overnight and then the solvent was removed in under vacuum. The product was extracted with 40 mL of hexane and the solution was filtered through a medium size glass frit Hexane was removed under reduced pressure leaving 7 81 g of product as a white solid Yield 95 percent Η(C6D6)δ-0.01 (s, 3H), 0.07 (s, 3H), 1.02 (s, IH), 110(s, 9H), 1.55 (m,
4H), 2.77 (m, 2H), 3.06 (m, 2H), 3.39 (s, IH), 5.59 (s, IH), 7.05 (t, IH, 37H H = 74 Hz), 7.27 (m, 2H), 7.40 (d, IH, 3JH-H = 74 HZ)
13C{ ]U}(C D ) δ -0.38, 0.52, 25.21, 34.11, 46.35, 49.55, 50.43, 100.07, 117.89, 119.85, 122.46, 125.51, 139.99, 146.46, 159.04
Figure imgf000100_0001
(8)
Preparation of N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(2-( 1 -pyrrolidinyl)- 1H- inden- 1 -yl)sιlanamιne, dilithium salt, (8). In the drybox 4.56 g ( 1451 mmol) of N- (1,1 -Dimethylethyl)- 1,1 -dimethyl- l-(2-(l -pyrrolidinyl)- lH-ιnden-l-yl)silanamιne was dissolved in 80 mL of hexane. To this solution 1875 mL (30 mmol) of rc-BuLi ( 1.6 M) was added dropwise Upon complete addition of the rc-BuLi the solution was stirred overnight The resulting precipitate was collected via filtration, washed with 50 mL of hexane and dried under reduced pressure to give 4.50 g of white solid. Yield 95 percent
Figure imgf000100_0002
(9) Preparation of dιchloro(N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a.7a-η)- 2-( 1 -pyrrolidinyl)- 1 H-inden- 1 -yl)sιlanamιnato-(2-)-N-)-tιtanιum, (9) N-( 1.1 - Di ethylethyO- 1.1 -dimethyl- 1 -(2-( 1 -pyrrolidinyl)- 1 H-inden- 1 -yl)sιianamιne, dilithium salt (4 50 g, 13 79 mmol) dissolved in 50 mL of THF was added within 2 minutes to a suspension of TιCl3(THF)3 (5 1 1 g, 13 79 mmol) in 60 mL of THF
After 1 houi of mixing, PbCh (2 49 g, 8 96 mmol) was added as a solid The reaction mixture was stirred for an additional 1 hour The solvent was then removed under reduced pressure The residue was extracted with 70 mL of toluene and filtered through a medium size glass frit The toluene was removed under reduced pressure and the residue was triturated with 50 mL of hexane The black-gray solid was collected by filtration, washed with hexane (2 x 30 mL) and then dried under reduced pressure 4 3 g of product was obtained as a brown-red solid Yield 72 percent
1 H (C0D6) δ 0 51 (s, 3H), 0 72 (s, 3H), 1 29 (m, 4H), I 41 (s. 9H), 2 99 (m,
2H), 3 17 (m, 2H), 5.99 (s, IH), 6 92 (t, I H, 37H n = 7 8 Hz), 7 12 (t, I H, 7H H = 7 7 Hz). 7 32 (d, I H. 37H H = 8 2 Hz), 7 70 (d, I H, 37H H = 8 6 Hz)
I 3C{ Η }(C6D6) δ 6 20, 6 77, 25 68, 32 89, 52 8 I , 61 61 , 84 45, 96 57, 125 77, 125 89, 126 79, 127 80, 133 47, 134 13, 160 00
Figure imgf000101_0001
( 10)
Preparation of (N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( 1 - pyrrolidinyl)- l H-ιnden-l -yl)sιlanamιnato-(2-)-N-)-dιmethyI-tιtanιum, ( 10) In the drybox 0 60 g of dιch!oro(N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1.2,3,3a,7a-η)-2-( 1 pyrrolidinyl)- IH-inden- 1 -yl)sιlanamιnato-(2-)-N-)-tιtanιum (139 mmol) was dissolved in 40 mL of Et2θ To this solution 0975 mL (292 mmol) of MeMgl (30 M) was added dropwise while stirring over a 5 minute period The solution changed color from deep brown to green-yellow After the addition of MeMgl was completed, the solution was stirred for 60 minutes The Et2θ was then removed under reduced pressure and the residue was extracted with hexane (2 x 20 mL), the solution was filtered and the filtrate was evaporated to dryness under reduced pressure to give 039 g (72 percent yield) of a yellow-orange solid
]H(C6D6)δ002(s, 3H), 056 (s, 3H), 068(s, 3H), 100 (s, 3H), 141 (m, 4H), 153 (s, 9H), 288 (m, 2H), 305 (m, 2H), 619 (s, IH), 689 (t, IH, 3Λ,H=77
Hz), 714 (t, 1H,3/HH = 85HZ), 743 (d, IH, 3JH H= 83 Hz), 756 (d, IH, 3 ,H =
13C{ Η}(C6D6) δ 633, 717, 2505, 3472, 5069, 5375, 5780.5801, 7890, 9444 12396 12487, 12529, 12667, 13016.13179 15886
Figure imgf000102_0001
(11)
Preparation of dιchloro(N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2.3,3a 7a-η)- 2-( 1 -pyrrolidinyl)- 1 H-inden- 1 -yl)sιlanamιnato-(2-)-N-)-zιrconιum N-( 1,1- Dimethylethyl)- 1 , 1 -dimethyl- 1 -(2-( 1 -pyrrolidinyl)- 1 H-inden- 1 -y Dsilanamine, dilithium salt (300 g, 960 mmol) was added slowly as a solid to a slurry of ZrCl4
(224 g, 960 mmol) in toluene (100 mL) This mixture was then allowed to stir overnight. After the reaction period the mixture was filtered and the volatiles were removed resulting in the isolation of the desired product as a gold microcrystal ne solid (3.02 g, 68 percent yield).
Η NMR (C6D6) δ 0.54 (s, 3 H). 0.69 (s. 3 H), 1.3- 1.5 (m, 4 H), 1.34 (s, 9 H). 3.0-3.1 (m, 4 H), 5.81 (s, 1 H), 6.98 (t, IH, 37HH=8.16 Hz), 7.10 (t, I H. 37HH=8.01 ), 7.32 (d, I H, 37HH=8.25 HZ). 7.70 (d, IH, /HH=8.49 HZ).
13C NMR (C6D6): δ 6.72, 7.09, 25.19, 33.35, 53.30, 56.04, 78 34, 90.38, 125 03, 126.31 , 126.47, 128.50, 129.84, 131.71 , 159. 18.
Figure imgf000103_0001
( 12)
Preparation of (N-( 1 , 1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3.3a,7a-η)-2-( 1 - pyrrolidinyl)- 1 H-inden- 1 -yl)sιlanamιnato-(2-)-N-)-dimethyl-zιrconιum, ( 12). Dιchloro(N-( 1.1 -dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-( I -pyrrolidinyl)- I H-ιnden- l -yl)silanaminato-(2-)-N-)-zιrconium (0.86 g, 1.81 mmol) was stirred in diethylether (50 mL) as MeMgBr (3.98 mmol, 1.33 mL of a 3.0 M solution in diethylether) was added slowly. This mixture was then allowed to stir overnight. After the reaction period the volatiles were removed and the residue was extracted and filtered using hexane. Removal of the hexane resulted in the isolation of the desired product as a pale yellow solid (0.51 g, 65 percent yield).
Η NMR (C6D6) δ -0.52 (s, 3 H), 0.36 (s, 3 H), 0.61 (s, 3 H). 0.71 (s. 3 H). 1.3- 1.6 (m, 4 H), 1.40 (s, 9 H), 2.8-3.0 (m, 2 H), 3.0-3.2 (m. 2 H). 5.92 (s, 1 H), 6 96 (t, IH. 3iHH = 8 10 Hz), 7.10 (t, I H, 3J ιι = 7 98 Hz), 7 36 (d, I H 37HH = 8.19 Hz), 7 68 (d, IH, 37HH = 8.25 Hz)
• C NMR (C6D6) δ 6.90, 7 45. 24.72, 34.51 , 35 13, 40.83. 53 86, 54.61 75 97, 88.62, 124.05, 124.45, 125 02, 127.26. 13 1.44, 159.02
Figure imgf000104_0001
(13)
Preparation of 2-ethoxy- 1 H-indene, lithium salt, ( 13) In the drybox 3 85 g (24 03 mmol) 2-ethoxy- lH-ιndene was dissolved in 100 mL of hexane. To this solution 19 5 mL (31.24 mmol) of n-BuLi ( 1 6 M) was added dropwise Upon complete addition of the π-BuLi the solution was stirred overnight The resulting off- white precipitate was collected via filtration, washed with 50 mL of hexane and dried under reduced pressure to give 3 91 g of product. Yield 98 percent.
Figure imgf000104_0002
(14)
Preparation of N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 -(2-ethoxy- 1 H-mden- 1 - yOsilanamine, ( 14). A solution of 2-ethoxy- l H-ιndene, lithium salt (3.91 g, 23 5 mmol) in 40 mL of THF was added dropwise to a 80 mL THF solution of N-(tert- butyl)-N-( l -chloro- 1 ,1 -dimethy lsilyOamine. The reaction mixture was stirred overnight and then solvent was removed in vacuum The product was extracted with 30 L of hexane and the solution was filtered through a medium size glass frit. Hexane was removed under reduced pressure leaving 6.45 g of product as a yellow oil Yield 94.7 percent.
lH(C6D6)δ0.09(s, 3H), 0.14 (s, 3H), 1.10 (m, IH), 1.09 (s,9H).1.10 (m. 3H), 3.39 (s, IH), 3.62 (m, 2H), 5.59 (s, IH), 7.09 (t. IH, 3/H-H = 7.3 Hz).7.27 (m, 2H).7.38(d, IH, 3iH-H = 7.4Hz).
13C{ lH)(C6D6) δθ.21, 0.41, 14.86, 34.08, 45.52.49.61, 65.49, 98.11. 119.20, 121.75, 123.04, 125.51, 138.28.144.80, 168.87.
Figure imgf000105_0001
(15)
Preparation of N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 -(2-ethoxy- 1 H-inden- 1 - yOsilanamine, dilithium salt, (15). In the drybox 6.45 g (22.28 mmol) of N-(l,l- dimethylethyl)- 1 , 1 -dimethyl- 1 -(2-ethoxy- 1 H-inden- 1 -yOsilanamine was combined with 120 mL of hexane. To this solution 32 mL (51.2 mmol) of π-BuLi (1.6 M) was added dropwise. Upon complete addition of the rc-BuLi the solution was stirred overnight. The resulting precipitate was collected via filtration, washed with hexane (2 x30 mL) to give 4.52 g (67 percent yield) of an off-white solid.
Figure imgf000106_0001
(16)
Preparation of dιchloro(N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)- 2-ethoxy- 1 H-inden- 1 -yl)sιlanamιnato-(2-)-N-)-tιtanιum, (16) N-( 1.1 -dimethy lethyl)- l,l-dιmethyl-l-(2-ethoxy-lH-ιnden-l-yl)sιlanamιne, dilithium salt (452 g, 150 mmol) dissolved in 40 mL of THF was added within 10 minutes to a suspension of TιCl3(THF)3 (556 g 150 mmol) in 70 mL of THF After 1 hour of mixing, PbCh (271 g, 975 mmol) was added as a solid The reaction mixture was stirred an additional hour The solvent was removed under reduced pressure The residue was extracted with 70 mL of toluene and filtered through a medium size glass frit Toluene was removed under reduced pressure and the residue was triturated with 40 mL of hexane The red-brown solid was collected by filtration, washed with hexane (2 x 25 mL) and then dried under reduced pressure The yield of product was 265 g, 44 percent
1H(C6D6)δ058(s, 3H),067(s, 3H), 102(t, 3H, 37H H = 68HZ), 138 (S,
9H), 357(m, IH) 419 (m, lH),603(s, IH), 696 (t, IH, 3/H n = 6 Hz), 711 (t, IH, 37H H = 78 HZ) 725 (d, IH, 37H H = 83 Hz), 755 (d, IH, 37H H = 82 Hz)
13C{ 1H}(C6D6) δ419, 489, 1446.3263, 6241, 6673, 8388, 9892, 12592, 12725 12736, 12858, 12958, 13204, 16408
HRMS(EI M+) calcd 4050565, found 4050563
Figure imgf000107_0001
(17)
Preparation of (N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2- cthoxy- 1 H-inden- 1 -yl)sιlanamιnato-(2-)-N-)-dιmethyl-tιtanιum, ( 17). In the drybox 0.40 g of dιchloro(N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-2-ethoxy- lH-ιnden- l -yl)silanamιnato-(2-)-N-)-tιtanιum (0.98 mmol) was dissolved in 50 mL of Et2θ To this solution 0.69 mL (2.07 mmol) of MeMgl (3 0 M) was added dropwise with stirring over a 5 minute period. After the addition of MeMgl was complete, the solution was stirred for 1 hour. Then the EtoO was removed under reduced pressure and the residue was extracted with hexane (3 x 35 mL), the solution was filtered and the filtrate was evaporated to dryness under reduced pressure to give 0.28 g (78 percent yield) of yellow solid.
i H (C6D6) δ -0.02 (s, 3H), 0.59 (s, 3H), 0.69 (s, 3H). 0.89 (s, 3H), 0.99 (t, 3H,
3 I-H = 6 9 HZ) 1.52 (s, 9H), 3.59 (m, 2H), 6.1 1 (s, IH), 6.92 (t, I H. 37H-H = 7.6 Hz), 7.14 (t, I H, 3Λ,.H = 8.5 Hz), 7.41 (d, IH, 37H-H = 8.3 Hz), 7.46 (d, IH, 3yH-H = 8.5 Hz)
13C{ ! H }(C6D6) δ 5.22, 5.78, 14.65, 34.60, 50.03, 57.52, 58.18, 65.69, 77. 18, 93.53, 124.66, 125.04, 125.39, 127.32, 126.89, 163.47.
Figure imgf000107_0002
( 18) Preparation of tert-buiy\( 1 H-2-ιndenyloxy)dιmethylsιlane, lithium salt, ( 18) In the drybox 5.0 g (20.2 mmol) of /er'-butyl( lH-2-mdenyloxy)dιmethyIsιlane was combined with 200 mL of hexane. To this solution 10 1 L (20.2 mmol) of
Figure imgf000108_0001
(2.0 M) was added dropwise. Upon complete addition of the «-BuLι the solution was stirred overnight The resulting precipitate was collected via by filtration, washed with hexane and dried under reduced pressure to give 4.20 g of product. Yield 82 percent.
Figure imgf000108_0002
( 19)
Preparation of (2-(( 1 -(/er/-butyl)- 1 , l-dιmethylsιlyl)oxy)- 1 H- 1 - ιndenyl)(chloro)dιmethyl-sιlane, ( 19). A solution of /er/-butyl( 1 H-2- ιndenyloxy)dιmethyIsιlane, lithium salt (4 20 g, 16.64 mmol) in 25 mL of THF was added within 30 minutes to a 50 mL THF solution containing SiMe2Cl2 (32.2 g, 249 mmol). After the addition was complete the reaction mixture was stirred overnight. The solvent was then removed under redeuced pressure. The residue was extracted with hexane and the solution was filtered. The solvent was then removed under reduced pressure leaving 5 44 g of product. Yield 96 percent
! H (C6D6) δ θ.03 (s, 3H), 0.15 (s, 3H), 1.52 (m, 4H), 3 14 (m, 4H), 3 43 (s, I H), 5 14 (s, I H), 7.24 (m, 2H), 7.23 (m,2H), 7.60 (m, 2H).
1 3C{ Η }(C6D6) δ -0.75, 0.48, 25.51 , 42.72, 50.52, 100.02, 103 77. 121.18,
121.29, 124.30, 124.70, 125.58, 141.29, 144.61 , 150.50.
Figure imgf000109_0001
(20)
Preparation of N-(/£-rr-butyl)-N-( 1 -(2-(( 1 -(r -butyl)- 1 , 1 -dimethylsilyOoxy)- 1 H-l -indenyl)- l,l-dιmethylsιlyl)amιne, (20) In the dry box 544 g of (2-(( \-{tert- butyl)- 1 , 1 -dimethylsilyOoxy)- 1 H- 1 -ιndenyl)(chloro)dιmethyl-sιlane ( 1592 mmol) was combined with 150 mL of hexane. To this solution NEt3 (195 g, 1925 mmol) and NH2/-B11 (141 g, 1925 mmol) were added and the solution was stirred overnight
The reaction mixture was filtered and the solvent was removed under reduced pressure to give 5.31 g of product Yield 88 percent.
lH(CDCl3)δ0 II (s, 3H),014 (s, 3H), 0.38 (s, 6H), 1.08 (s,9H), 125 (s, 9H), 343 (s, IH), 588 (s, IH), 714 ( , IH), 7.23 (m,2H), 758 (m, IH).
Figure imgf000109_0002
(21)
Preparation of N-(/<?rr-butyl)-N-( 1 -(2-(( 1 -( rf-butyl)- 1 , 1 -dimethylsiIyOoxy)- lH-!-ιndenyl)-l.l-dιmethyIsιlyi)amιne. dilithium salt, (21). N-( -butyl)-N-(l-(2-(( (/e/ -butyl)-l,l-dιmethylsιlyl)oxy)-lH-l-ιndenyl)-l,l-dιmethylsιlyl)amιne (300 g, 8 63 mmol) was stirred in hexane ( 100 mL) as n-BuLi ( 17 4 mmol, 8.70 L of a 2.0 M solution in cyciohexane) was added slowly. This mixture was then allowed to stir overnight during which time a white solid precipitated. After the reaction period the desired product was collected via by filtration, washed with hexane, and dried under vacuum resulting in the isolation of a white solid which was used without further purification or analysis ( 1 58 g, 51 percent yield).
Figure imgf000110_0001
(22)
Preparation of dιchloro(N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a,7a-η)-
2-( Dtmethyl-/-butylsιloxy)- 1 H-inden- 1 -yl)sιlanamιnato-(2-)-N-)-tιtanιum, (22) N- ( 1.1 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(2-dιmethyl-f-butylsιloxy- 1 H-inden- 1 - yOsilanamine, dilithium salt ( 1.58 g, 4 40 mmol) in THF (30 mL) was added dropwise to a slurry of TιCl3(THF)3 ( 1 63 g, 4 40 mmol) in THF ( 100 mL) at 0°C This mixture was then allowed to stir at room temperature for 2 hours PbCh (0 65 g,
2.35 mmol) was then added to the mixture as a solid which was then allowed to stir for an additional hour After the reaction period the volatiles were removed and the residue was extracted and filtered using toluene. Removal of the toluene resulted in the isolation of a red/orange residue which was redissolved in hexane and filtered. Removal of the hexane resulted in the isolation of the desired product as an orange solid ( 1.27 g, 62 percent yield).
! H NMR (CDCl ) δ 0.34 (s, 3 H), 0 44 (s. 3 H), 0 75 (s, 3 H), 0.87 (s. 3H),
0.98 (s, 9 H), 1 40 (s, 9 H), 6.56 (s, 1 H), 7.21 (t, 3 ι n = 68 Hz, 1 H), 7 35 (t, 37H n = 795 Hz, 1 H), 756(d,
Figure imgf000111_0001
I H), 765 (d, 37H H = 873 Hz 1 H)
I3C NMR (CDCI3) δ -377, -338, 440, 514, 1880, 2584, 3239 6253 8617 10444, 12548, 12678, 12694, 12811,12910.13126, 16107
Figure imgf000111_0002
(23)
Preparation of (N-( 11 -Dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2.3,3a,7a- η)-2- (dιmethyI-f-butylsιloxy)-lH-ιnden-I-yl)sιlanamιnato-(2-)-N-)-dιmethyl-tιtanιum, (23) Dιchloro(N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 -(( 1 ,2,3,3a.7a-eta)-2-(dιmethyl-/- butylsιloxy)-lH-ιnden-l-yl)sιlanamιnato-(2-)-N-)-tιtanιum (035 g, 074 mmol) was stirred in diethylether (75 mL) as MeMgBr (150 mmol, 050 mL of a 30 M solution in diethylether) was added slowly This mixture was then allowed to stir for 2 hours After the reaction period the volatiles were removed and the residue was extracted and filtered using hexane Removal of the hexane resulted in the isolation of the desired product as a yellow oil (021 g, 65 percent yield)
l NMR (C6D6) δ 033 (s, 3 H) 021 (s, 3 H), 025 (s, 3 H), 065 (s.3 H),
073 (s, 3 H) 099 (s 9 H), 112 (s, 3 H), 159 (s, 9 H), 655 (s, 1 H), 694 (t, 37H H=78Hz, 1 H), 719(t, 37HH = 74HZ, 1 H), 747 (d, 37H H = 83 Hz, IH), 753 (d, 37H H=85HZ, IH) 1 C NMR (C6D6)δ -3.61,-3.48, 5.62, 5.97, 18.84,2515,34.60.5213,57.79, 58.25,80.38, 100.38, 12470, 125.13, 125.56, 127.26, 12856, 159.87.
Polymerization data for catalyst systems comprising metal complexes of this invention are presented in the table that follows.
Polymenzation Data
I
Figure imgf000113_0001
a) cocatalyst is B(CgF5)3
c) melt index (g / 10 mm) tl) g polymer / g Ti
X-ray structure determination of dιchloro(N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethy I- l -(( 1 ,2.3, 3a,7a-η)-2-dιmethy lamino- 1 H-mden- l -yl)sιlanamιnato-(2-)-N-)-tιtanιum.
Data Collection
A dark purple block-shaped crystal of dimensions 0.21 x 0 17 x 0 06 mm was immersed in oil, Paratone N, Exxon, and mounted on a thin glass fiber The crystal was transferred to a Siemens SMART PLATFORM diffractometer equipped with a graphite monochromatic crystal, a MoKα radiation source (1 = 0.71073 A), a CCD (charge coupled device) area detector which is kept at 5 078 cm from the crystal The crystal was bathed in a cold nitrogen stream tor the duration of data collection (- 100 C) Three sets of 20 frames each were collected covering three perpendicular sectors of space using the ω scan method and with a ten second exposure time Integration of the frames followed by reflection indexing and least squares refinement produced a crystal orientation matrix and a monclinic lattice
Data collection was set up to collect a total of 1631 frames in four different run^> covering more than one full hemisphere of data. Frame scan parameters are summarized in the following table
Scan Scan Frames Exposure
Run 2Θ ω φ χ axis width (°) ( # ) time (sec.)
1 -29 -26.00 0.00 54.68 2 -0 3 626 30
2 -29 -21.00 90 00 54 68 2 -0.3 455 30
3 -29 -23 00 180 0 54 68 2 -0.3 250 30
0
4 -29 -23.00 45 00 54 68 2 -0 3 250 30
5 -29 -26.00 0 00 54 68 2 -0.3 50 30 The last run (# 5) is the rcmeasurement of the first 50 frames from run numbei 1 This is done to monitor crystal and diffractometer stability and to correct for any crystal decay
Diffractometer setup includes a 0 8 mm collimator providing an X-ray beam of 0 8 mm in diameter Generator power was set at 50 KV and 35 mA. Program SMART' was usecj for diffractometer control, fi me scans, indexing, orientation matrix calculations, least squares refinement of cell parameters, crystal faces measurements and the actual data collection Program ASTRO ' was used to set up data collection strategy
Data Preparation
All 1381 crystallographic raw data frames were read by program SAINT ' and integrated using 3D profiling algorithms The resulting data were reduced to produce hkl reflections and their intensities and estimated standard deviations The data were corrected for Lorentz and polarization effects A total of 7842 reflections were collected representing a range of 2 55 to 1 70 redundancy level and have an Rsvm value range of 2 9 percent, at the lowest 2θ shell of reflections, to 3 1 percent at the highest 2Θ shell of reflections (55 °) Crystal decay correction was applied and was less than 1 percent. The unit cell parameters were refined by least squares of the setting angles of 5415 reflections Unit cell parameters arc
a = 8.3173(3) A a = 91 324( 1) °
b = 9.1847(3) A b = 91 541(1 ) °
c = 13.2048(5) A g = 103 384( 1 ) °
V = 980 54(6) A1 Absorption corrections were applied using program SADABS- according to
Blessing3 Absorption coefficient was 0 77 mm"' and minimum and maximum transmissions were 0 812 and 0 962, respectively
Data preparation was carried out using program XPREP' The space group
was determined to be P l (# 2) based on systematic absences XPREP provided the following crystallographic parameters 4362 unique reflections (Rιn, = 1 94 percent) with indices - 1 1 < h < 10, -S < k < 12, - 17 < / < 18
Structure solution and Refinement
The structure was solved by direct methods in SHELXTL5^ from which the positions of all of the non-H atoms were obtained The structure was refined, also in SHELXTL5, using full-matrix least-squares refinement The non-H atoms were refined with anisotropic thermal parameters and all of the H atoms were located by a Difference Fourier map and refined without any constraints In the final cycle of refinement, 3639 observed reflections with I > 2s(I) were used to refine 313 parameters and the resulting R ] , WRT and S (goodness of fit) were 2 93 percent, 7 40 percent and
1 061 , respectively A correction for secondary extinction was applied with x =
0 0025( 12) The maximum and minimum residual electron density peaks in the final
Difference Fourier map were 0 376 and -0 369, respectively The refinement was carried out using F^ rather than F values Rj is calculated to provide a reference to the conventional R value but its function is not minimized Additionally, wR2 is the functions that is minimized and not R\
STRUCTURE SOLUTION AND REFINEMENT
The structure was solved by direct methods in SHELXTL5 from which the positions of all of the non-H atoms were obtained The structure was refined, also in SHELXTL5, using full-matrix least-squares refinement The non-H atoms were refined with anisotropic thermal parameters and all of the H atoms were located by a Difference Fourier map and refined without any constraints. In the final cycle of refinement. 4838 observed reflections with I > 2σ(I) were used to refine 432 parameters and the resulting R ] , WR2 and S (goodness of fit) were 3.13 percent, 7. 17 percent and 1 .023, respectively.
A correction for secondary extinction was applied with x = 0.0018(7). The maximum and minimum residual electron density peaks in the final Difference Fourier map were 0.324 and -0.368, respectively. The refinement was carried out using F2 rather than F values. R] is calculated to provide a reference to the conventional R value but its function is not minimized. Additionally, wR2 is the functions that is minimized and not Rj .
The linear absorption coefficient, atomic scattering factors and anomalous- dispersion corrections were calculated from values from the International Tables for X-ray Crystallography International Tables for X-ray Crystallography ( 1974). Vol. IV. p. 55. Birmingham: Kynoch Press. (Present distributor, D. Reidel, Dordrecht.).
Figure 1 shows the crystal structure of dichloro(N-( 1 , 1 -dimethylethyl)- 1 , 1 - dimethy 1- 1 -(( 1 ,2,3,3a,7a-η)-2-dimethyIamino- 1 H-inden- 1 -yl)silanaminato-(2-)-N-)- titanium.
Relevant functions used for the foregoing structure determinations are given below.
R i = A(IIF0I - IFcll) / AIF0I
wR2 = [A[w(Fo2 - Fc2)2] / A[w(Fo2)2]] 1 /2
Rjnt. = A IFo2 - F0 2(mean)l2/ A[F0 2]
Λ 9 9 9 W
S = [A[w(Fo - Fc )~] / (n-p)] u~ where n is the number of reflections and p is the total number of parameters refined
w= l/[s2 (Fo 2)+(0.0370*p)2 +0.3 l *p], p = [max(Fo 2,0)+ 2* Fc 2]/3 X-ray structure determination of (N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 - (( 1 ,2,3,3a,7a-η)-2-ethoxy- 1 H-inden- 1 -yl)sιlanamιnato-(2-)-N-)-dιmethyl-tιtanιum.
Data Collection.
A translucent, red, platy crystal of ONSiTiCh i 7H25 having approximate dimensions of 0.4 x 0.2 x 0.06 mm was mounted using oil, (Paratone-N, Exxon) on a glass fiber. Ail measurements were made on an Enraf-Nonius CAD4 diffractometer with graphite monochromated Mo-Kα radiation.
Cell constants and an orientation matrix for data collection, obtained from a least-squares refinement using the setting angles of 25 carefully centered reflections in the range 18 2 < 2Θ < 23.6° corresponded to a C-centered monoc nic cell with dimensions
a = 28.874(9) A b = 9.924(3)) A β = 121 .99(2) ° c = 16.294(3)A V = 3959(2) A3
For Z = 8 and F W = 406.28, the calculated density is 1 36 g/cm3 Based on the systematic absences of
hkl: h + k ≠ 2n
hOl: 1 ≠ 2n
packing considerations, a statistical analysis of intensity distribution, and the successful solution and refinement of the structure, the space group was determined to be-
C2/c (#15) The data were collected at a temperature of -120 ± 1 °C using the ω- θ scan technique to a maximum 2Θ value of 49.9°. Omega scans of several intense reflections, made prior to data collection, had an average width at half-height of 0.25° with a take-off angle of 2.8°. Scans of ( 1.00 + 0.35 tan θ) ° were made at a variable speed of 3.0 - 16.0 °/min (in omega). Moving-crystal moving counter background measurements were made by scanning an additional 25 percent above and below the scan range. The counter aperture consisted of a variable horizontal slit with a width ranging from 2.0 to 2.5 mm and a vertical slit set to 2.0 mm. The diameter of the incident beam collimator was 0.7 mm and the crystal to detector distance was 21 cm. For intense reflections an attenuator was automatically inserted in front of the detector.
Data Reduction
Of the 3786 reflections which were collected, 3705 were unique Rjnt = 0.041 ).
The intensities of three representative reflection were measured after every 90 minutes of X-ray exposure time. No decay correction was applied.
The linear absorption coefficient, μ. for Mo-Kα radiation is 7.7 cm" ' . An analytical absorption correction was applied which resulted in transmission factors ranging from 0.85 to 0.95. The data were corrected for Lorentz and polarization effects. A correction for secondary extinction was applied (coeffficient = 1.34465e- 08).
Structure and Solution and Refinement
The structure was solved by direct methods (SHELXS86: Sheldrick, G.M.
( 1985). In: "Crystallographic Computing"3 (Eds G.M. Sheldrick, C. Kruger and R. Goddard) Oxford Univeristy Press, pp. 175- 189) and expanded using Fourier techniques (DIRDIF94: Beurskens, P.T., Admiraal, G., Beurskens, G., Bosman, W. P., de Gelder, R.. Israel. R. and Smits, J.M.M. ( 1994). The DIRDIF-94 program system, Technical Report of the Crystallography Laboratory, University of Nijmegan, The Netherlands). The nonhydrogen atoms were refined anisotropically. Hydrogen atoms were included in idealized positions but not refined. The final cycle of full- matrix least-squares refinement11 was based on 2223 observed reflections (I > 3.00σ(D) and 209 variable parameters and converged (largest parameter shift was 0.01 times its esd) with unweighted and weighted agreement factors of:
R = l\\Fo\ - \Fc\\ / ∑\Fo\ = 0.040
Figure imgf000120_0001
The standard deviation of an observation of unit weight0 was 1 47 The weighting scheme was based on counting statistics. Plots of ∑w(|Fo| - |Fc|)2 versus |Fo|, reflection order in data collection, sin θ/λ and various classes of indices showed no unusual trends. The maximum and minimum peaks on the final difference Fourier map corresponded to 0.37 and -0.35 e"/A ' 3 , respectively
Neutral atoms scattering factors were taken from Cromer and Waber (Cromcr. D T. & Waber, J T , "International Tables for X-Ray Crystallography", Vol, IV. The Kynoch Press, Birmingham, England. Table 2.2 A ( 1974)). Anomalous dispersion effects were included in Fcalc (Ibers, J.A. & Hamilton, W C , Acta Crystallogr , 17, 781 ( 1964)); the values for Δf and Δf" were those of Creagh and McAuley (Creagh, D.C. & McAuley, W. J ; "International Tables for Crystallography., Vol C , (A.J.C Wilson, ed.), Kluwer Academic Publishers. Boston, Table 4.2.6.8, pages 219-222 ( 1992)) The values for the mass attenuation coefficients are those of Creagh and Hubbel (Creagh, D.C. & Hubbell, J.H.; "International Tables for Crystallography", Vol. C, (A.J.C. Wilson, ed.), Kluwer Academic Publishers, Boston, Table 4.2.4.3, pages 200-206 ( 1992)). All calculations were performed using the teXsan (teXsan: Crystal Structure Analysis Package, Molecular Structure Corporation ( 1985 & 1992)) crystallographic software package of Molecular Structure Corporation.
(a) Least-Squares:
Function minimized: ∑w(|Fo| - |Fc|)2 where w = 4Fo2 σ2(Fo) σ2(Fo2)
s- (C + R-B) + (pFo- γ σ2(Fo2) =
Lp-
S - Scan rate
C = Total integrated peak count R - Ratio of scan time to background counting time B - Total background count Lp = Lorentz-polaπzation factor p = p- factor
(b) Standard deviation of an observation of unit weight
Figure imgf000121_0001
where No = number of observations Nv = number of variables
Figure 2 shows the crystal structure of (N-( 1 , 1 -dimethylethyl)- 1 , 1 -dimethyl- 1 - a,7a-η)-2-ethoxy- 1 H-inden- 1 -yl)sιlanamιnato-(2-)-N-)-dιmethyl-tιtanιum

Claims

WHAT IS CLAIMED IS
1 A metal complex corresponding to the formula
Figure imgf000122_0001
where M is a metal from one of Groups 3 to 13 of the Periodic Table of the Elements, the Ianthanides or acti des, which is in the +2, +3 or +4 formal oxidation state and which is π-bonded to one cyclopentadienyl group (Cp) which is a cyclic, delocalized, π-bound ligand group having 5 substituents (R ),-T where J IS zero, 1 oi
2, RB, Rc , RD and Z, where RA, RB, Rc and RD are R groups, and where
T is a heteroatom which is covalently bonded to the Cp ring, and to R^ when j is 1 or 2, and when j is 0, T is F, Cl, Br, or I, when j is 1 , T is O or S, or N or P and RA has a double bond to T, when j is 2, T is N or P, and where
R independently each occurrence is hydrogen, or, is a group having fiom I to 80 nonhydrogen atoms which is hydrocarbyl, hydrocarbylsilyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilylhydrocarbyl, hydrocarbylamino, dι(hydrocarbyl)amιno, hydrocarbyloxy, each RA optionally being substituted with one or more groups which independently each occurrence is hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, dι(hydrocarbyisιlyl)amιno, hydrocarbylamino, dι(hydrocarbyl)amιno, dι(hydrocarbyl)phosphιno, hydrocarbylsulfido, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having from I to 20 nonhydrogen atoms, or a noninterfering group having from 1 to 20 nonhydrogen atoms, and each of RB, R and RP is hydrogen, or is a group having from 1 to 80 nonhydrogen atoms which is hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl. hydrocarbylsilyl. hydrocarbylsilylhydrocarbyl, each RP, R or P optionally being substituted with one or more groups which independently each occurrence is hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, dι(hydrocarbylsιlyl)amιno, hydrocarbylamino, dι(hydrocarbyl)amιno, dι(hydrocarbyl)phosphιno, hydrocarbylsulfido, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy- substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having from 1 to 20 nonhydrogen atoms, or a noninterfering group having from 1 to 20 nonhydrogen atoms; or, optionally, two or more of R^, RP. RC and P are covalently linked with each other to form one or more fused rings or ring systems having from 1 to 80 nonhydrogen atoms for each R group, the one or more fused rings or ring systems being unsubstituted or substituted with one or more groups which independently each occurrence are hydrocarbyloxy, hydrocarbylsiloxy. hydrocarbylsilylamino, dι(hydrocarbylsιlyl)amιno, hydrocarbylamino, dι(hydrocarbyl)amιno, dι(hydrocarbyI)phosphιno, hydrocarbylsulfido, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy- substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having from 1 to 20 nonhydrogen atoms, or a noninterfering group having from 1 to 20 nonhydrogen atoms;
Z is a divalent moiety bound to both Cp and M via σ-bonds, where Z comprises boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprises nitrogen, phosphorus, sulfur or oxygen,
X is an anionic or dianionic ligand group having up to 60 atoms exclusive of the class of ligands that are cyclic, delocalized, π-bound ligand groups,
X' independently each occurrence is a neutral Lewis base gating compound having up to 20 atoms, p is zero. 1 or 2. and is two less than the formal oxidation state of M. when X is an anionic ligand, when X is a dianionic ligand group, p is 1 ; and
q is zero, 1 or 2
2. The metal complex of Claim 1 corresponding to the formula.
Figure imgf000124_0001
where R^, R- , R^ and R^ are R groups, each of which independently is hydrogen, or is a group having from 1 to 80 nonhydrogen atoms which is hydrocarbyl. halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl, hydrocarbylsilylhydrocarbyl, each of R \ R^, R^ and R^ optionally being substituted with one or more groups which independently each occurrence is hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, dι(hydrocarbylsιlyl)amιno, hydrocarbylamino, dι(hydrocarbyl)amιno, di(hydrocarbyI)phosphιno, hydrocarbylsulfido, hydrocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy- substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydrocarbyl having from 1 to 20 nonhydrogen atoms, or a noninterfering group having from 1 to 20 nonhydrogen atoms; or, optionally, two or more of R^. R^, R R^, RA and RB are covalently linked with each other to form one or more fused rings or ring systems having from 1 to 80 nonhydrogen atoms tor each R group, the one or more fused rings or ring systems being unsubstituted or substituted with one or more groups which are hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, dι(hydrocarbylsιlyl)amιno. hydrocarbylamino, dι(hydrocarbyl)amιno, dι(hydrocarbyl)phosphιno, hydrocarbylsulfido. hydiocarbyl, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino-substituted hydrocarbyl, hydrocarbylsilyl or hydrocarbylsilylhydiocarbyl having from 1 to 20 nonhydrogen atoms, or a noninterfeπng group having from 1 to 20 nonhydrogen atoms
3 The metal complex of Claim 1 or Claim 2 wherein RA , hydrocarbyl, hydrocarbylsilyl, hydrocarbyloxy-substituted hydrocarbyl, hydrocarbylamino- substituted hydrocarbyl and T is O or N
4 The metal complex of Claim 3 wherein R^ IS hydrocarbyl or hydrocarbylsilyl and T is O or N
5 The metal complex of Claim 4 wherein RA I hydrocarbyl or hydiocarbylsilyl and T is O
6 The metal complex of Claim 3 wherein the (RA),-T group dimethylamino, diethylamino, methylcthylamino, methvlphenylamino, dipropylamino, dibutylamino, pipeπdinyl, morpholinyl, pyrrolidinyl, hexahydro-lH-azepιn- 1-yl, hexahydro- 1 (2H)-azocιny I, octahydro- 1 H-azonin- 1 -yl, octahydro- 1 (2H)-azecιnyl, methoxy, ethoxy, propoxy, methylethyloxy, 1 , 1 -dιmethyethyloxy, tπmethylsiloxy or 1 , 1 -dιmethylethy](dιmethylsιlyl)oxy,
7 The metal complex of Claim 4 wherein the (RA).-T group is methoxy, ethoxy, propoxy, methylethyloxy, 1 , 1 -dιmethyethyloxy, tπmethylsiloxy, 1 , 1 - dιmethylethyl(dιmethyisιlyl)oxy
8 The metal complex of Claim 1 or Claim 2 wherein the one or more fused rings or ring systems contain one or more ring heteroatoms which are N, 0, S, or P
9 The metal complex of Claim 8 wherein the ring heteroatoms are N or
O
10. The metal complex of Claim 9 wherein each ring heteroatom is N.
The metal complex of Claim 2 corresponding to the formula.
Figure imgf000126_0001
where the symbols are as previously defined.
12. The metal complex of Claim 1 I corresponding to the formula:
Figure imgf000126_0002
where the symbols arc as previously defined.
13. The metal complex of one of Claims 1 - 12 where -Z- is -Z*-Y-. with Z bonded to Cp and Y bonded to M, and
Y is -O-, -S-, -NR*-, -PR*-;
Z* is SiR*2, CR*2, SiR*2SiR*2. CR*2CR*2, CR*=CR*, CR*2SιRΛ 2, CR*2SiRXCR*2. SiR*2CR*2SiR*2. CR*2CR*2SiR*2. CR*2CR* CR*2- or GeR*2; and
R* independently each occurrence is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R* having up to 20 nonhydrogen atoms, and optionally, two R groups from Z (when R is not hydrogen), or an R+ group from Z and an R 1- group from Y form a ring system,
where p is 2, q is zero, M is in the +4 formal oxidation state, and X is independently each occurrence methyl, benzyl, tπmethylsilylmethyl. allyl, pyrollyl or two X groups together are 1 ,4-butane-dιyl, 2-butene-l ,4-dιyl, 2,3-dιmethyI-2-butene- 1 ,4-dιyl, 2-methyl-2-butene- 1 ,4-dιyl, or xylyldiyl.
14 The metal complex of one of Claims 1 - 12 where -Z- is -Z*-Y-, with Z* bonded to Cp and Y bonded to M, and
Figure imgf000127_0001
Z * is SιR*2- CRA 2, SιR*2SιR* . CR*2CR ' 2, CR+=CR*, CR*2SιR*2,
CR*2SιR*2CR*2- SιR*2CR*2S l R X- CR*2CR*2SιR*2- CR*2CR*2CR*2- or GeR*2, and
R* independently each occurrence is hydrogen, or a member selected from hydrocarbyl. hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R* having up to 20 nonhydrogen atoms, and optionally, two R* groups from Z (when R* is not hydrogen), or an R* group from Z and an R+ group from Y form a ring system,
where p is 1 , q is zero, M is in the +3 formal oxidation state, and X is 2-(N.N- dιmethyl)amιnobenzyl, 2-(N,N-dιmethylamιnomethyl)phenyl, allyl, methallyl, tπmethylsilylallyl
15 The metal complex of one of Claims 1 - 12 where -Z- is -Z*- Y-, with Z* bonded to Cp and Y bonded to M, and
Y is -O-, -S-, -NR' -, -PR*-, Z* is SιR*2, CR 2, SιR*2SιR*2, CR*2CR^2- CR*=CR*, CR*2SιR*2, CR*2SιR*2CRX, SιR*2CR*2SlR*2- CR*2CR*2SιR*2- CR* CR* CR*2. or Ge *2' ar)d
R* independently each occurrence is hydrogen, or a member selected from hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl, and combinations thereof, said R* having up to 20 nonhydrogen atoms, and optionally, two R* groups from Z (when R* is not hydrogen), or an R+ group from Z and an R* group from Y form a ring system,
when p is 0, q is 1 , M is in the +2 formal oxidation state, and X' is 1 ,4- diphenyl- 1 ,3-butadιene, 1 ,3-pentadιene or 2,4-hexadιene
16 The metal complex of one of Claims 1 - 15 where M is a metal from one of Groups 3-6, one of Groups 7-9 or one of Groups 10- 12
17 The metal complex of Claim 16 where M is a metal from one of Groups
3-6
18 The metal complex of Claim 16 where M is a metal from one of Groups
7-9
19 The metal complex of Claim 16 where M is a metal from one of Groups 10-12
20 The metal complex of Claim 17 where M is a metal from Group 4
21 The metal complex of Claim 20 where M is Ti
22 The metal complex of Claim 20 where M is Zr
23 The metal complex of Claim 21 where M is Ti is the +4 formal oxidation state
24. The metal complex of Claim 21 where M is Ti is the +3 formal oxidation state.
25. The metal complex of Claim 21 where M is Ti is the +2 formal oxidation state.
26. The metal complex of Claim 22 where M is Zr is the +4 formal oxidation state.
27. The metal complex of Claim 22 where M is Zr is the +2 formal oxidation state.
28. The metal complex of one of Claims 13-27 where Y is -NR*.
29. The metal complex of Claim 28 where R* is a group having a primary or secondary carbon atom bonded to N.
30. The metal complex of Claim 29 where R* is cyclohexyl or isopropyl.
31. The metal complex of Claim 23 corresponding to the formula:
Figure imgf000129_0001
The metal complex of Claim 23 corresponding to the formula
Figure imgf000130_0001
The metal complex of Claim 23 corresponding to the formula: %
Figure imgf000130_0002
The metal complex of Claim 23 corresponding to the formula:
Figure imgf000130_0003
35. The metal complex of Claim 23 corresponding to the formula.
Figure imgf000131_0001
36. The metal complex of Claim 23 corresponding to the formula
Figure imgf000131_0002
37. The metal complex of Claim 23 corresponding to the formula.
Figure imgf000131_0003
38. The metal complex of Claim 23 corresponding to the formula:
Figure imgf000132_0001
39 The metal complex of Claim 23 corresponding to the formula:
Figure imgf000132_0002
40 The metal complex of Claim 23 corresponding to the formula
Figure imgf000133_0001
41 A catalyst system for olefin polymerization prepared from catalyst system components comprising.
(A) a catalyst component comprising a metal complex of one of Claims I - 40, and
(B) a cocatalyst component comprising an activating cocataiyst wherein the molar ratio of (A) to (B) is from 1 10,000 to 100- 1 , or activation of (A) by use of an activating technique
42. The catalyst system of Claim 41 further comprising (C) an aluminum organometalhc component.
43 The catalyst system of Claim 42 wherein the aluminum organometalhc component comprises an alumoxane, an aluminum alkyl or a combination thereof
44 The catalyst system of one of Claims 41 -43 wherein the cocatalyst component comprises an organoboron compound which is nonionic or ionic
45 The catalyst system of Claim 44 wherein the cocatalyst component comprises tπs(pentafluorophenyl)borane
46. The catalyst system of Claim 45 wherein the cocatalyst component comprises an alumoxane and tris(pentafluorophenyl)borane in a molar ratio from 1 : 1 to 5: 1.
47. The catalyst system of one of Claims 41-46 further comprising (D) a support component comprising a support material which is a polymer, an inorganic oxide, a metal halide, or a mixture thereof.
48. A catalyst system for olefin polymerization prepared from catalyst system components comprising:
(A) a catalyst component comprising a metal complex of one of Claims 1 - 40; and
(B) a cocatalyst component comprising an activating cocatalyst wherein the molar ratio of (A) to (B) is from 1 : 10,000 to 100: 1
wherein the metal complex is in the form of a radical cation.
49. A process for the polymerization of olefins comprising contacting one or more C2-20 α-olefins under polymerization conditions with a catalyst system of one of Claims 41 -48.
50. The process of Claim 49 wherein ethylene, propylene and optionally a nonconjugated diene are copolymerized.
51. The process of Claim 49 wherein ethylene, propylene, or ethylene and propylene, and one or more C4.20 α-olefins are copolymerized.
52. The process of one of Claims 49-51 wherein the process is carried out in solution.
53. The process of one of Claims 49-51 wherein the process is carried out in the gas phase.
54 The process of one of Claims 49-51 wherein the process is carried out in a slurry
55 A high temperature solution polymerization process for the polymerization of olefins comprising contacting one or more C2-20 α-olefins under polymerization conditions with a catalyst system of one of Claims 41 -48 at a temperature from about 100°C to about 250°C
56 The process of Claim 55 wherein the temperature is from about 120°C to about 200°C
57 The process of Claim 56 wherein the temperature is from about I 50°C to about 200°C
58 A polyolefin product produced by the process of one of Claims 49-57
59 The polyolefin product of Claim 55 wherein the product has from 0 01 to 3 long chain branches per 1000 carbon atoms
60 The polyolefin product of Claim 58 wherein the product is a copolymer composition which has a comonomer partitioning factor Cpf which is equal to or greater than 1 10 or a molecular weight partitioning factor Mpf which is equal to or greater than 1 15, or a comonomer partitioning factor Cpf which is equal to or greater than 1 10 and a molecular weight partitioning factor Mpf which is equal to or greater than 1.15
61 The polyolefin product of Claim 60 wherein the copolymer composition has a comonomer partitioning factor Cpf which is equal to or greater than 1 20 or a molecular weight partitioning factor Mpf which is equal to or greater than 1 30, or a comonomer partitioning factor Cpf which is equal to or greater than 1.20 and a molecular weight partitioning factor Mpf which is equal to or greater than 1 30
62. A cyclopentadienyl-containing ligand of one of Claims 1 -40 where the ligand is in the form of.
(A) a free base with 2 protons capable of being deprotonated;
(B) a dilithium salt;
(C) a magnesium salt: or
(D) a mono or disilylated dianion.
63 Use of a ligand of Claim 62 for synthesis to produce a metal complex of one of Claims 1 -40.
64 Use of a ligand of Claim 62 for synthesis to produce a metal complex comprising a metal from one of Groups 3 to 13 of the Periodic Table of the Elements. the Ianthanides or actinides. and from 1 to 4 of the ligands
PCT/US1997/013171 1996-08-08 1997-07-28 2-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process WO1998006728A1 (en)

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JP10509760A JP2000516608A (en) 1996-08-08 1997-07-28 2-heteroatom-substituted cyclopentadienyl-containing metal complex and olefin polymerization method
NZ333877A NZ333877A (en) 1996-08-08 1997-07-28 metal complex of a substituted indene derivative and use of the complex in an olefin polymerization process
EP97937033A EP1021454A1 (en) 1996-08-08 1997-07-28 2-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process
HU9904148A HUP9904148A3 (en) 1996-08-08 1997-07-28 2-heteroatom substituted cyclopentadienyl containing metal complexes and process for olefin polymerization
CA002262377A CA2262377A1 (en) 1996-08-08 1997-07-28 2-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process
AU39647/97A AU716659B2 (en) 1996-08-08 1997-07-28 2-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process
BR9711115A BR9711115A (en) 1996-08-08 1997-07-28 Metallic complex catalyst system for olefin polymerization process for olefin polymerization polymerization process in high temperature solution binder polyolefin product containing cyclopentadienyl and use of a binder
SK152-99A SK15299A3 (en) 1996-08-08 1997-07-28 2-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process
NO990546A NO990546L (en) 1996-08-08 1999-02-05 3-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process

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EP0940408A1 (en) * 1998-03-04 1999-09-08 Bayer Aktiengesellschaft Metalorganic compounds
WO2000043406A1 (en) * 1999-01-25 2000-07-27 Chisso Corporation Metallocene compounds as catalyst components for olefin polymerization
US6617407B1 (en) 1999-04-29 2003-09-09 The Dow Chemical Company Bis(n,n-dihydrocarbylamino)-substituted cyclopentadienes and metal complexes thereof
US6555634B1 (en) 1999-05-13 2003-04-29 The Dow Chemical Company Di- and tri-heteroatom substituted indenyl metal complexes
US6646071B1 (en) 1999-05-13 2003-11-11 The Dow Chemical Company Metal complexes containing bridging heteroatom for olefin-polymerization-process
US6420299B1 (en) 1999-06-04 2002-07-16 Dow Global Technologies Inc. Boron-substituted cyclopentadienes and metal complexes thereof
US6825295B2 (en) 1999-12-10 2004-11-30 Dow Global Technologies Inc. Alkaryl-substituted group 4 metal complexes, catalysts and olefin polymerization process
SG120079A1 (en) * 1999-12-10 2006-03-28 Dow Global Technologies Inc Substituted group 4 metal complexes catalysts and olefin polymerization process
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US6515155B1 (en) * 1999-12-10 2003-02-04 Dow Global Technologies Inc. Substituted group 4 metal complexes, catalysts and olefin polymerization process
WO2001042315A1 (en) * 1999-12-10 2001-06-14 Dow Global Technologies Inc. Substituted group 4 metal complexes, catalysts and olefin polymerization process
US6730754B2 (en) 2000-01-18 2004-05-04 Basell Polyolefine Gmbh Process for producing substantially amorphous propylene-based polymers
WO2001053361A1 (en) * 2000-01-19 2001-07-26 Borealis Technology Oy Siloxy-substituted monocyclopentadienyl ligated constrained geometry olefin polymerisation catalysts
WO2001053362A1 (en) * 2000-01-19 2001-07-26 Borealis Technology Oy Metallocene catalysts comprising monocyclic siloxy substituted cyclopentadienyl group(s) for the polymerisation of olefins
US7141690B2 (en) 2002-02-08 2006-11-28 Sumitomo Chemical Company, Limited Transition metal complexes, ligands, polymerization catalysts for olefins, and process for production of olefin polymers
US7241927B2 (en) 2002-02-08 2007-07-10 Sumitomo Chemical Company, Limited Transition metal complexes, ligands, catalysts for olefin polymerization, and process for production of olefin polymers
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US6927264B2 (en) 2003-05-28 2005-08-09 Dow Global Technologies Inc. Metal complexes and polymerization process using same
WO2011017092A1 (en) 2009-07-28 2011-02-10 Univation Technologies, Llc Polymerization process using a supported constrained geometry catalyst
US9382361B2 (en) 2014-03-21 2016-07-05 Exxonmobil Chemical Patents Inc. Process to produce ethylene propylene copolymers
US10773246B2 (en) 2015-01-06 2020-09-15 Scg Chemicals Co., Ltd. SiO2-layered double hydroxide microspheres and methods of making them
US11643331B2 (en) 2015-01-06 2023-05-09 Scg Chemicals Co., Ltd. SiO2-layered double hydroxide microspheres and methods of making them
US11053269B2 (en) 2016-05-12 2021-07-06 Scg Chemicals Co., Ltd. Unsymmetrical metallocene catalysts and uses thereof
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