CA2815543A1 - N-heterocyclic carbene complexes, their preparation and use - Google Patents

Abstract

N-heterocyclic carbene complexes of the formula (I) is disclosed, wherein the radicals have the meanings as defined in the invention. The preparation and the use as catalysts employed in a C-C, C-O, C-N or C-H bond formation reaction of said complexes are also disclosed.

Description

N-heterocyclic carbene complexes, their preparation and use BACKGROUND OF THE INVENTION
The present invention relates to N-heterocyclic carbene complexes, a method for their preparation and their use as catalysts.
DESCRIPTION OF THE RELATED ART
In 1968 H.W. Wanzlick and K. Ofele independently reported the first direct synthesis of metal complexes with N-heterocyclic carbenes (NHCs) as ligands. At that time, no one would have been able to predict the role these ligands would play a few decades later.
Especially the NHC complexes of Pd(II) find broad application in modern organic and organometallic chemistry. The advantages of NHCs like thermal stability, low toxicity, insensitivity against oxygen over other ligands like phosphanes have allowed the appli-cation of NHC complexes in a number of different coupling reactions, e.g.
Heck, Sonogashira, Suzuki-Miyaura, Stille, Hartwig-Buchwald coupling, and others. In par-ticular, the Suzuki-Miyaura reaction today plays an important role due to the stability, availability and low toxicity of the employed boronic acids.
In addition to the use in catalysis, NHC complexes are also useful in many other fields like medical applications, nanoparticles, supramolecular chemistry, self-assembly, pho-tochemistry, liquid crystals, polymerisation and electronically active materials.
Besides the great number of advantages of these special ligands, the synthesis of saturated NHC complexes remains challenging. A. J. Arduengo, R. Krafczyk and R.
Schmutzler describe in Tetrahedron 1999, 55, 14523-14534 the synthesis of imidazoly-lidenes, imidazolinylidenes and imidazolidines starting from glyoxal via the correspond-ing diimines and diamine dihydrochlorides. Subsequently, the diamine dihydrochlorides are converted into the corresponding imidazolinium salts by reaction with an ortho for-mate as C1 building block. Reduction of the imidazolinium salts with lithium aluminium hydride leads to imidazolidines, whereas deprotonation with potassium hydride leads to the corresponding imidazolin-2-ylidenes. Nevertheless, this methodology does in par-ticular not allow the formation of unsymmetrically substituted NHCs.
B. A. Bhanu Prasad and S. R. Gilbertson describe in Org. Lett. 2009, 11, 3710-3713 a one-pot synthesis of unsymmetrical NHC ligands from N-(2-iodoethyl)arylamine salts.
This route is limited to the formation of NHCs with certain substituents.

It is known, to employ isonitrile metal complexes for the formation of either acyclic or cyclic carbenes.
K. Bartel and W. P. Fehlhammer describe in Angew. Chem. Int. Ed. 1974, 13, 599-the formation of oxazolidinylidene and perhydrooxazinylidene complexes of Pd, Pt and Au by reaction of 2-, and 3-hydroxyalkyl isocyanides with metal compounds.
U. Plaia and W. P. Fehlhammer describe in J. Am. Chem. Soc. 1985, 107, 2171-the preparation of hexakis(oxazolidin-2-ylidene)cobalt(III) and ¨
rhodium(III).
M. Tamm and F. E. Hahn describe in Coord. Chem. Rev. 1999, 182, 175-209 the formation of carben complexes from coordinated 13-functional phenyl isocyanides.
R. A. Michelin, L. Zanotto, D. Braga, P. Sabatino and R. J. Angelici describe in lnorg.
Chem. 1988, 27, 85-92 the synthesis of cyclic aminooxycarbene complexes of Pt(II) via a cyclization reaction of isocyanide complexes with 2-bromoethanol.
I. Yu, C. J. Wallis, B. O. Patrick, P. L. Diaconescu and P. Mehrkhodavandi in doi:10.1021/om100841j reported a remotely related reaction, using a primary amine and a strain-activated isonitrile/phosphane chelate on iron.
R. A. Michelin, L. Zanotto, D. Braga, P. Sabatino and R. J. Angelici describe in lnorg.
Chem. 1988, 27, 93-99 the synthesis of cyclic diaminocarbene complexes of Pd(II) and Pt(II) via a cyclization reaction of isocyanide complexes with 2-bromoethylamine.
R. A. Michelin, A. J. L. Pombeiro and M. F. C. Guedes da Silva report in Coord. Chem.
Rev. 2001, 218, 75-112 on aminocarbene complexes derived from nucleophilic addition to isocyanide ligands.
The method described in the tree last-mentioned documents delivers NHCs that are unsubstituted at one nitrogen atom and only alkyl substituents could be attached to this nitrogen atom subsequently. The synthesis of the free NHC often requires long or-ganic-synthetic steps and the attachment of the thus synthesized NHC ligand to the metal is often difficult and requires additional synthetic effort.
There is still a great need for an effective method that allows the preparation N,N'-disubstituted NHC-complexes, and in particular unsymmetrically disubstituted NHC-complexes. The metal-NHC-complexes should be air-stable and easy to handle.

It has now been found that, surprisingly, this object is achieved by reaction of substi-tuted w-haloalkylammonium salts or w-(alkoxycarbonyl)alkylammonium salts with con-veniently accessible isonitrile complexes.
SUMMARY OF THE INVENTION
The present invention relates to a process for preparing compounds of the general formula (I) ,, R5 R. R7 n (I) M
where n is = 0 or 1, M is a metal atom containing group, R1 is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl, R2 is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl, wherein R1 and R2 do not both stand for hydrogen, R3 and R4 are independently selected from hydrogen and in each case unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dialkyl)amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl)amino, (dicycloalkyl)amino, hetero-cycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl)amino, (diheterocycloalkyl)amino, aryl, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl)amino and (dihetaryl)amino, or R3 and R4 together with the carbon atom to which they are bound are 0=0, or R3 is a group 0-R3a and for n = 0 R4 and R7 stand for the bond equivalent of a double bond between the carbon atoms carrying R4 and R7, respectively or for n = 1 R4 and R5 stand for the bond equivalent of a double bond between the carbon atoms carrying R4 and R5, respectively, where R3a is a group bound to the oxygen via a carbon atom, silicon atom, sulfur atom, phosphorus atom, boron atom or titanium atom, R5, R6, R7 and R8 are independently selected from hydrogen and in each case unsub-stituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dialkyl)amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl)amino, (dicycloal-kyl)amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monohet-erocycloalkyl)amino, (diheterocycloalkyl)amino, aryl, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (mono-hetaryl)amino and (dihetaryl)amino, wherein the two radicals R2 and R8 may also form together with the N atom to which R2 is bound a 3- to 12-membered, unsubstituted or substituted nitro-gen heterocycle which may optionally have 1, 2 or 3 further heteroatoms or heteroatom containing groups independently selected from 0, N, NRa and S as ring members, wherein Ra is hydrogen, alkyl, cycloalkyl or aryl, or wherein if n = 0, R4 and R7 also may stand for the bond equivalent of a double bond between the carbon atoms carrying R4 and R7, which comprises al) the reaction of an isonitrile complex of the general formula (11) R1¨NC¨M
(11) in which R1 and M have one of the meanings given above, with a compound of the general formulae (111) or (111a) +Z

n 2 Y 5 - NH Y -n N

X-(111) (111a) in which n, R2, R3, R4, R5, R6, R7 and R8 have one of the meanings given above, X- is an anion equivalent, and Y is a leaving group, or if R3 and R4 together with the carbon atom to which they are bound are 0=0 then Y is a group O-Ya, where Ya is unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted or substituted arylcarbonyl or unsubstituted or substituted alkyl carbonyl, and bl) optionally, if R3 and R4 together with the carbon atom to which they are bound are 0=0, subjecting the product obtained in step al) to a further reaction with a com-pound R3a-Z, where Z is a leaving group, in the presence of a base to obtain a compound of the formula (I) where R3 is a group 0-R3a and for n = 0 R4 and R7 stand for the bond equivalent of a double bond between the carbon atoms bound to R4 and R7 or for n = 1 R4 and R5 stand for the bond equivalent of a double bond between the carbon atoms bound to R4 and R5, or a2) the reaction of an isonitrile complex of the general formula II
R1¨NEC¨M (II) where R1 and M have one of the meanings given above, with a compound of the general formula (V) ,rµ
ri10 I
11 (V) R2N/". )R

where R2, R3 and R8 have one of the meanings given above; and R1 and R" are independently selected from Ci-C4-alkyl or R1 and R" together are linear C2-C4-alkylene which may be substituted by one or more Ci-C4 alkyl radicals;
to give an intermediate compound of the formula (VI) R11\

R10 ----oR (VI) R
H, /N------(N,R2 Ri M
and b2) the treatment of the intermediate compound of the formula (VI) with an acid, wherein in compound (I) obtained according to this variant n is 0, and R4 and stand for the bond equivalent of a double bond between the carbon atoms carry-ing R4 and R7;
or a3) the reaction of an isonitrile complex of the general formula II
R1¨NEC¨M (II) where R1 and M have one of the meanings given above, with a compound of the general formulae (111b) or (111c) Isisty&+ ZR2 .1444-Y& /R2 EWG

(111b) (IIIc) where R2, R4, R7 and R8 have one of the meanings given above;
X- is an anion equivalent; and EWG is (C(0)R14, C(0)0R14, NO2, S(0)R14 or S(0)2R14, where R14 is hydrogen, alkyl, cycloalkyl or aryl;
wherein in compound (I) obtained according to variant a3) n is 0 and R3 is CH2-EWG.
In a first aspect, the invention provides a process for preparing compounds of the gen-eral formula (I) ix 7 N, Ri-- -R-, (1) where n is = 0 or 1, M is a metal atom containing group, R1 is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl, R2 is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl, wherein R1 and R2 do not both stand for hydrogen, R3 and R4 are independently selected from hydrogen and in each case unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dialkyl)amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl)amino, (dicycloalkyl)amino, hetero-cycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl)amino, (diheterocycloalkyl)amino, aryl, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl)amino and (dihetaryl)amino, or R3 and R4 together with the carbon atom to which they are bound are C=0, or R3 is a group O-R3a and for n = 0, R4 and R7 stand for the bond equivalent of a double bond between the carbon atoms carrying R4 and R7, respectively or R3 is a group O-R3a and for n = 1, R4 and R5 stand for the bond equivalent of a double bond between the carbon atoms carrying R4 and R5, respectively, where R3a is a group bound to the oxygen via a carbon, silicon, sulfur, phospho-rus, boron or titanium atom, R5, R6, R7 and R8 are independently selected from hydrogen and in each case unsub-stituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dialkyl)amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl)amino, (dicycloal-kyl)amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monohet-erocycloalkyl)amino, (diheterocycloalkyl)amino, aryl, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (mono-hetaryl)amino and (dihetaryl)amino, wherein the two radicals R2 and R8 may also form together with the N atom to which R2 is bound and the carbon atom to which R8 is bound a 3- to 12-membered, unsub-stituted or substituted nitrogen heterocycle which may optionally have 1, 2 or further heteroatoms or heteroatom containing groups independently selected from 0, N, NRa and S as ring members, wherein Ra is hydrogen, alkyl, cycloalkyl or aryl, which comprises al) the reaction of an isonitrile complex of the general formula (11) Ri¨NEC¨M (11) in which R1 and M have one of the meanings given above, with a compound of the general formulae (111) or (111a) Z

n NH2 n N

(111) (111a) in which n, R2, R3, R4, R5, R6, R7 and R8 have one of the meanings given above, X- is an anion equivalent, and Y is a leaving group, or if R3 and R4 together with the carbon atom to which they are bound are 0=0 then Y is a group O-Ya, where Ya is unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted or substituted arylcarbonyl or unsubstituted or substituted alkyl carbonyl, and bl) optionally, if R3 and R4 together with the carbon atom to which they are bound are 0=0, subjecting the product obtained in step al) to a further reaction with a com-pound R3a-Z, where Z is a leaving group, in the presence of a base to obtain a compound of the formula (I) where R3 is a group 0-R3a and for n = 0 R4 and R7 stand for the bond equivalent of a double bond between the carbon atoms bound to R4 and R7 or for n = 1 R4 and R5 stand for the bond equivalent of a double bond between the carbon atoms bound to R4 and R5.
According to a special embodiment, the process of the invention is used for the forma-tion of unsymmetrically substituted compounds of the formula (I). In this embodiment, preferably R1 and R2 have different meanings.
A first variant is a process for preparing compounds of the formula (I-A.1) or (I-A.2) --- Ri R2 NzN

M M
(1-A.1) (1-A.2) where M, R1, R2, R5, R6, R7 and R8 have a meaning as defined above and in the following, R3 and R4 are independently selected from hydrogen and in each case unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dialkyl)amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl)amino, (dicycloalkyl)amino, hetero-cycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl)amino, 10 (diheterocycloalkyl)amino, aryl, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl)amino and (dihetaryl)amino, which comprises al) the reaction of an isonitrile complex of the general formula (II) R¨NEC¨M (11) in which R1 and M have one of the meanings defined above and in the following, with a compound of the general formulae (111) or (111a) +/R2 n NH2 Y 5 - Y _n N
R R6 _ R6 R6 H
X
(111) (111a) in which n, R2, R3, R4, R5, R6, R7 and R8 have one of the meanings defined above and in the following, X- is an anion equivalent, and Y is a leaving group.
A second variant is a process for preparing compounds of the general formula (l-6.1) or (1-6.2) ix C) R8 ---(1-6.1) (1-6.2) where M, R1, R2, R5, R6, R7 and R8 have a meaning as defined above and in the following, which comprises al) the reaction of an isonitrile complex of the general formula (II) R¨NEC¨M (II) in which R1 and M have one of the meanings as defined above and in the follow-ing, with a compound of the general formulae (111-6.1), (111-6.1.a), (111-6.2) or (111-6.2.a) X I /R2 o Hi 0 R7 R8 z R2 Ya-07\(+N NZR Ya-OZ(+ a-rNR2 Ya-OV( R7 R8 2 YO

X
(111-6.1) (111-6.1.a) (111-6.2) (111-6.2.a) in which R2, R5, R6, R7 and R8 have one of the meanings as defined above and in the fol-lowing, X- is an anion equivalent, and Ya is unsubstituted or substituted alkyl, unsubstituted or substituted aryl, un-substituted or substituted arylcarbonyl or unsubstituted or substituted alkyl carbonyl.
Insofar the keto compounds of the general formula (1-6.1) or (1-6.2) are able to form tautomers, those tautomers are also part of the invention.
A third variant is a process for preparing compounds of the general formula (I-0.1) or (I-0.2) 3a 3aR ¨0 R8 R ¨07 i/N R2 R1/N ¨R2 /N
(1-0.1) (1-0.2) where M, R1, R2, R3a, R6, R7 and R8 have a meaning as defined above, which comprises al) the reaction of an isonitrile complex of the general formula (II) R¨NEC¨M (11) in which R1 and M have one of the meanings given above, with a compound of the general formulae (111-0.1), (111-0.1 .a), (111-0.2) or (III-C.2.a) 0 R\ 1R8 R2 :IR\4R8 2 0 0 H
+
ya-ONH2 ya_o NZR NHõ 2 Ya-OZ(N\R2 R x H R8 x- R
H 6 - H R6 Ili H R8 (111-0.1) (111-0.1.a) (III-C.2) (III-C.2.a) in which R2, R6, R7 and R8 have one of the meanings given above, X- is an anion equivalent, and Ya is unsubstituted or substituted alkyl, unsubstituted or substituted aryl, un-substituted or substituted arylcarbonyl or unsubstituted or substituted alkyl carbonyl, and bl) subjecting the product obtained in step al) to a further reaction with a compound R3a-Z, where Z is a leaving group, in the presence of a base.
In a second aspect, the invention provides a process for preparing compounds of the general formula (I-E) (compounds of the formula I, where n is 0 and R4 and R7 stand for the bond equivalent of a double bond between the carbon atoms carrying R4 and R7) R\ R8 ___________________________________ r R1/N\/NR2 (I-E) M
where M is a metal atom containing group, R1 is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl, R2 is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl, wherein R1 and R2 do not both stand for hydrogen, R3 is selected from hydrogen and in each case unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dialkyl)amino, cycloalkyl, cycloalkoxy, cyclo-alkylthio, (monocycloalkyl)amino, (dicycloalkyl)amino, heterocycloalkyl, hetero-cycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl)amino, (diheterocycloal-kyl)amino, aryl, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hetaryl, hetary-loxy, hetarylthio, (monohetaryl)amino and (dihetaryl)amino, R8 is selected from hydrogen and in each case unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dialkyl)amino, cycloalkyl, cycloalkoxy, cyclo-alkylthio, (monocycloalkyl)amino, (dicycloalkyl)amino, heterocycloalkyl, hetero-cycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl)amino, (diheterocycloal-kyl)amino, aryl, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hetaryl, hetary-loxy, hetarylthio, (monohetaryl)amino and (dihetaryl)amino, wherein the two radicals R2 and R8 may also form together with the N atom to which R2 is bound a 3- to 12-membered, unsubstituted or substituted nitrogen heterocycle which may optionally have 1, 2 or 3 further heteroatoms or heteroatom containing groups independently selected from 0, N, NRa and S as ring members, wherein Ra is hydrogen, alkyl, cycloalkyl or aryl which comprises a2) the reaction of an isonitrile complex of the general formula II
Ri¨NEC¨M (II) where R1 and M have one of the meanings given above, with a compound of the general formula (V) r,10 ,rµ

2NIRiRi I (V) where R2, R3 and R8 have one of the meanings given above; and R1 and R11 are independently selected from C1-C4-alkyl or R1 and R11 together are linear C2-C4-alkylene which may be substituted by one or more, e.g. 1, 2, 3, 4, 5 or 6 Ci-C4 alkyl radicals;
to give an intermediate compound of the formula (VI) R11\

R_........, _R8 rµ -----0-(VI) R
H, N---/N,R2 M
in which R1, R2, R3, R8, R10, R11 and M are as defined above;
and 5 b2) the treatment of the intermediate compound of the formula (VI) with an acid.
According to a special embodiment, the process of the invention according to the sec-ond aspect is used for the formation of unsymmetrically substituted compounds of the formula (I-E). In this embodiment, preferably R1 and R2 have different meanings.
In a third aspect, the invention provides a process for preparing compounds of the general formula I-F (compounds of the formula!, where n is 0 and R3 is CH2-EWG) _______________________________ R4 EWG y R87 ( R
(1-F) RiNNs¨R2 M
where R1, R2, R4, R7, R8, M and EWG have one of the meanings given above, which comprises a3) the reaction of an isonitrile complex of the general formula II, Ri¨NEC¨M (11) where R1 and M have one of the meanings given above with a compound of the general formulae (111b) or (111c) + ZR2 EWG NH2 .1444-Y& /R2 N
EWG

(111b) (1110 where EWG, R2, R4, R7 and R8 have one of the meanings given above; and X- is an anion equivalent.
According to a special embodiment, the process of the invention according to the third aspect is used for the formation of unsymmetrically substituted compounds of the for-mula (I-F). In this embodiment, preferably R1 and R2 have different meanings.
In a further aspect, the invention provides new compounds of the general formula (I).
In a further aspect, the invention provides new compounds of the general formula (VI).
In a further aspect, the invention provides a catalyst, comprising or consisting of a compound of the general formula (I).
In a further aspect, the invention provides the use of a compound of the general for-mula (I) as or in a catalyst employed in a C-C, 0-0, C-N or C-H bond formation reac-tion.
According to a special embodiment, the compound of the general formula (I) is used in a C-C coupling reaction, selected from the Suzuki reaction, Heck reaction, Sonogashira reaction, Stille reaction, Hartwig-Buchwald reaction and Kumada reaction.
According to a further special embodiment, the compound of the general formula (I) is used in a hydrogenation, hydroformylation, hydrosilylation, Hartwig-Buchwald reaction or amide a-arylation.
DESCRIPTION OF THE INVENTION
For the purpose of the present invention the term N-heterocyclic carbene (NHC) de-notes compounds that can be present in the form of different resonance structures, represented e.g. by structures with a divalent carbon atom as well as ylide type struc-tures.
/ +/
--- N --- N - N
+\ \ \

Preferred embodiments of the compounds of the general formula (I) are compounds of the formulae (I-A.1), (I-A.2), (I-B.1), (I-B.2), (1-0.1) and (1-0.2), as shown above and in the following. All definitions regarding compounds of the general formula (I) are also applicable for compounds of the formulae (I-A.1), (I-A.2), (I-B.1), (I-B.2), (1-0.1) and (I-0.2), unless explicitly defined otherwise. Preferred embodiments of the compounds of the general formula (I) are also compounds of the formulae (I-E) and (I-F), as shown above and in the following. All definitions regarding compounds of the general formula (I) are also applicable for compounds of the formulae (I-E) and (I-F), unless explicitly defined otherwise.
In the context of the present invention, single bonds are used to represent the M-Ccarbene interactions in the compounds of the formulae (I) and (VI).
The expression "halogen" denotes in each case fluorine, bromine, chlorine or iodine, particularly chlorine, bromide or iodine.
In the context of the invention, the expression "unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dialkyl)amino, cycloalkyl, cycloalkoxy, cycloalkyl-thio, (monocycloalkyl)amino, (dicycloalkyl)amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl)amino, (diheterocycloalkyl)amino, aryl, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl)amino and (dihetaryl)amino" represents unsubstituted or substituted al-kyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubsti-tuted or substituted (monoalkyl)amino, unsubstituted or substituted (dialkyl)amino, un-substituted or substituted cycloalkyl, unsubstituted or substituted cycloalkoxy, unsubsti-tuted or substituted cycloalkylthio, unsubstituted or substituted (monocycloalkyl)amino, unsubstituted or substituted (dicycloalkyl)amino, unsubstituted or substituted hetero-cycloalkyl, unsubstituted or substituted heterocycloalkoxy, unsubstituted or substituted heterocycloalkylthio, unsubstituted or substituted (monoheterocycloalkyl)amino, unsub-stituted or substituted (diheterocycloalkyl)amino, unsubstituted or substituted aryl, un-substituted or substituted aryloxy, unsubstituted or substituted arylthio, unsubstituted or substituted (monoaryl)amino, unsubstituted or substituted (diaryl)amino, unsubstituted or substituted hetaryl, unsubstituted or substituted hetaryloxy, unsubstituted or substi-tuted hetarylthio, unsubstituted or substituted (monohetaryl)amino and unsubstituted or substituted (dihetaryl)amino.
In the context of the present invention, the expression "alkyl" comprises straight-chain or branched alkyl groups. Alkyl is preferably C1-C30-alkyl, more preferably Ci-C2o-alkyl and most preferably CI-Cu-alkyl. Examples of alkyl groups are especially methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl.
The expression alkyl also comprises alkyl radicals whose carbon chains may be inter-rupted by one or more nonadjacent groups which are selected from -0-, -S-, -NRb-, -C(=0)-, -S(=0)- and/or -S(=0)2-. Rb is preferably hydrogen, alkyl, cycloalkyl, hetero-cycloalkyl, aryl or hetaryl.
Substituted alkyl groups may, depending on the length of the alkyl chain, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably each inde-pendently selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkylcarbonyloxy, carbamoyl, 503H, sulfonate, sulfamino, sulfamide, amidino, where El and E2 are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. Cycloalkyl, heterocycloalkyl, aryl and hetaryl substituents of the alkyl groups may in turn be unsubstituted or substituted; suitable substituents are the sub-stituents mentioned below for these groups.
Carboxylate and sulfonate respectively represent a derivative of a carboxylic acid func-tion and a sulfonic acid function, especially a metal carboxylate or sulfonate, a carbox-ylic ester or sulfonic ester function or a carboxamide or sulfonamide function.
The above remarks regarding alkyl also apply to the alkyl moiety in alkoxy, alkylthio (=
alkylsulfanyl), monoalkylamino and dialkylamino.
In the context of the present invention, the term "cycloalkyl" denotes a mono-, bi- or tricyclic hydrocarbon radical having usually from 3 to 20, preferably 3 to 12, more pref-erably 5 to 12, carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclopentadecyl, norbornyl, bicyclo[2.2.2]octyl or adamantyl.
Substituted cycloalkyl groups may, depending on the ring size, have one or more (e.g.
1, 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from alkyl, alkoxy, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, car-boxylate, alkylcarbonyloxy, carbamoyl, 503H, sulfonate, sulfamino, sulfamide, amidino, NE3E4 where E3 and E4 are each independently hydrogen, alkyl, cycloalkyl, hetero-cycloalkyl, aryl or hetaryl. In the case of substitution, the cycloalkyl groups preferably bear one or more, for example one, two, three, four or five, C1-C6-alkyl groups. Exam-ples of substituted cycloalkyl groups are especially 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 2-, 3-and 4-propylcyclohexyl, 2-, 3- and 4-isopropylcyclohexyl, 2-, 3- and 4-butylcyclohexyl, 2-, 3- and 4-sec.-butylcyclohexyl, 2-, 3- and 4-tert-butylcyclohexyl, 2-, 3-and 4-methylcycloheptyl, 2-, 3- and 4-ethylcycloheptyl, 2-, 3- and 4-propylcycloheptyl, 2-, 3-and 4-isopropylcycloheptyl, 2-, 3- and 4-butylcycloheptyl, 2-, 3- and 4-sec-butylcycloheptyl, 2-, 3- and 4-tert-butylcycloheptyl, 2-, 3-, 4- and 5-methylcyclooctyl, 2-, 3-, 4- and 5-ethylcyclooctyl, 2-, 3-, 4- and 5-propylcyclooctyl.
The above remarks regarding cycloalkyl also apply to the cycloalkyl moiety in cycloalkoxy, cycloalkylthio (= cycloalkylsulfanyl), monocycloalkylamino and dicycloal-kylamino.
In the context of the present invention, the term "aryl" refers to mono- or polycyclic aromatic hydrocarbon radicals. Aryl usually is an aromatic radical having 6 to 24 car-bon atoms, preferably 6 to 20 carbon atoms, especially 6 to 14 carbon atoms as ring members. Aryl is preferably phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenan-threnyl, naphthacenyl, chrysenyl, pyrenyl, coronenyl, perylenyl, etc., and more prefera-bly phenyl or naphthyl.
Substituted aryls may, depending on the number and size of their ring systems, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from alkyl, alkoxy, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkylcarbonyloxy, carbamoyl, SO3H, sulfonate, sulfamino, sulfamide, amidino, NE5E6 where E5 and E6 are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. The alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl and hetaryl substituents on the aryl may in turn be unsubstituted or substituted. Reference is made to the substituents mentioned above for these groups. The substituents on the aryl are preferably selected from alkyl, alkoxy, haloalkyl, haloalkoxy, aryl, fluorine, chlorine, bromine, cyano and nitro. Substi-tuted aryl is more preferably substituted phenyl which generally bears 1, 2, 3, 4 or 5, preferably 1, 2 or 3, substituents.
Substituted aryl is preferably aryl substituted by at least one alkyl group ("alkaryl", also referred to hereinafter as alkylaryl). Alkaryl groups may, depending on the size of the aromatic ring system, have one or more (e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more than 9) alkyl substituents. The alkyl substituents may be unsubstituted or substituted. In this regard, reference is made to the above statements regarding unsubstituted and substi-tuted alkyl. In a preferred embodiment, the alkaryl groups have exclusively unsubsti-tuted alkyl substituents. Alkaryl is preferably phenyl which bears 1, 2, 3, 4 or 5, pref-5 erably 1, 2 or 3, more preferably 1 or 2, alkyl substituents.
Aryl which bears one or more radicals is, for example, 2-, 3- and 4-methylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl, 2,4-, 10 2,5-, 3,5- and 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3-and 4-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-, 3-and 4-sec-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-sec-butylphenyl, 2,4,6-tri-sec-15 butylphenyl, 2-, 3- and 4-tert-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-tert-butylphenyl and 2,4,6-tri-tert-butylphenyl; 2-, 3- and 4-methoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-, 3- and 4-ethoxyphenyl, 2,4-, 2,5-, 3,5-and 2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-, 3- and 4-propoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropoxyphenyl, 2-, 3- and 4-isopropoxyphenyl, 2,4-, 2,5-, 3,5-and 20 2,6-diisopropoxyphenyl and 2-, 3- and 4-butoxyphenyl; 2-, 3- and 4-chlorophenyl, (2-chloro-6-methyl)phenyl, (2-chloro-6-ethyl)phenyl, (4-chloro-6-methyl)phenyl, (4-chloro-6-ethyl)phenyl.
The above remarks regarding aryl also apply to the aryl moiety in aryloxy, arylthio (=
arylsulfanyl), monoarylamino and diarylamino.
In the context of the present invention, the expression "heterocycloalkyl"
comprises nonaromatic, unsaturated or fully saturated, cycloaliphatic groups having generally 5 to 8 ring atoms, preferably 5 or 6 ring atoms. In the heterocycloalkyl groups, compared to the corresponding cycloalkyl groups, 1, 2, 3, 4 or more than 4 of the ring carbon atoms are replaced by heteroatoms or heteroatom-containing groups. The heteroatoms or heteroatom-containing groups are preferably selected from -0-, -S-, -NRe-, -C(=0)-, -S(=0)- and/or -S(=0)2-. Re is preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. Heterocycloalkyl is unsubstituted or optionally bears one or more, e.g. 1, 2, 3, 4, 5, 6 or 7, identical or different radicals. These are preferably each independ-ently selected from alkyl, alkoxy, alkylamino, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkylcarbonyloxy, carbamoyl, SO3H, sulfonate, sulfamino, sulfamide, amidino, NE5E6 where E6 and E6 are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. Examples of heterocycloalkyl groups are especially pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyre-zolidinyl, oxazolidinyl, morpholinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperaz-inyl, tetrahydrothiophenyl, dihydrothien-2-yl, tetrahydrofuranyl, dihydrofuran-2-yl, tetra-hydropyranyl, 2-oxazolinyl, 3-oxazolinyl, 4-oxazolinyl and dioxanyl.
Substituted heterocycloalkyl groups may, depending on the ring size, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably each independ-ently selected from alkyl, alkoxy, alkylthio, cycloalkyl, heterocycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkylcarbonyloxy, carbamoyl, SO3H, sulfonate, sulfamino, sul-famide, amidino, NE7E8 where E7 and E8 are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. In the case of substitution, the hetero-cycloalkyl groups preferably bear one or more, for example one, two, three, four or five, Ci-C6-alkyl groups.
The above remarks regarding heterocycloalkyl also apply to the heterocycloalkyl moi-ety in heterocycloalkoxy, heterocycloalkylthio (= heterocycloalkylsulfanyl), monohetero-cycloalkylamino and diheterocycloalkylamino.
In the context of the present invention, the expression "hetaryl" (heteroaryl) comprises heteroaromatic, mono- or polycyclic groups. In addition to the ring carbon atoms, these have 1, 2, 3, 4 or more than 4 heteroatoms as ring members. The heteroatoms are preferably selected from oxygen, nitrogen, selenium and sulfur. The hetaryl groups have preferably 5 to 18, e.g. 5, 6, 8, 9, 10, 11, 12, 13 or 14, ring atoms.
Monocyclic hetaryl groups are preferably 5- or 6-membered hetaryl groups, such as 2-furyl (furan-2-y1), 3-furyl (furan-3-y1), 2-thienyl (thiophen-2-y1), 3-thienyl (thiophen-3-y1), selenophen-2-yl, selenophen-3-yl, 1H-pyrrol-2-yl, 1H-pyrrol-3-yl, pyrrol-1-yl, imidazol-2-yl, imidazol-1-yl, imidazol-4-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-thiadiazol-2-yl, 4H41,2,4]-triazol-3-yl, 1,3,4-triazol-2-yl, 1,2,3-triazol-1-yl, 1,2,4-triazol-1-yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yland 1,2,4-triazin-3-yl.

Polycyclic hetaryl groups have 2, 3, 4 or more than 4 fused rings. The fused-on rings may be aromatic, saturated or partly unsaturated. Examples of polycyclic hetaryl groups are quinolinyl, isoquinolinyl, indolyl, isoindolyl, indolizinyl, benzofuranyl, isoben-zofuranyl, benzothiophenyl, benzoxazolyl, benzisoxazolyl, benzthiazolyl, benzoxadia-zolyl, benzothiadiazolyl, benzoxazinyl, benzopyrazolyl, benzimidazolyl, benzotriazolyl, benzotriazinyl, benzoselenophenyl, thienothiophenyl, thienopyrimidyl, thiazolothiazolyl, dibenzopyrrolyl (carbazolyl), dibenzofuranyl, dibenzothiophenyl, naphtho[2,3-b]thiophenyl, naphtha[2,3-b]furyl, dihydroindolyl, dihydroindolizinyl, dihydroisoindolyl, dihydroquinolinyl and dihydroisoquinolinyl.
Substituted hetaryl groups may, depending on the number and size of their ring sys-tems, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are pref-erably each independently selected from alkyl, alkoxy, alkylthio, cycloalkyl, hetero-cycloalkyl, aryl, hetaryl, fluorine, chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate, alkylcarbonyloxy, carbamoyl, SO3H, sul-fonate, sulfamino, sulfamide, amidino, NE9E1 where E9 and El are each independ-ently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. Halogen substituents are preferably fluorine, chlorine or bromine. The substituents are preferably selected from CI-Cs-alkyl, Ci-C6-alkoxy, hydroxyl, carboxyl, halogen and cyano.
The above remarks regarding hetaryl also apply to the hetaryl moiety in hetaryloxy, hetarylthio, monohetarylamino and dihetarylamino.
Preferably, in the compounds of the general formula (I) the metal atom containing group M comprises a metal selected from groups 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13 of the Periodic Table. Preferred metals are Ti, Zr, Cr, Mo, W, Re, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, In and B.
Particular preference is given to compounds of the general formula (I), wherein M is a Pd(II), Pt(II) or Au(I) containing group.
Suitable groups M are in principle groups of the formula LyMe-, wherein Me is a metal, L is a ligand and y is an integer which depends on the valence and type of the metal and on the number of coordination sites occupied by each of the ligands L.
Suitable ligands L are independently selected from among F, Cl, Br, I, CO, isonitriles, nitriles, amines, carboxylates, acetylacetonate, hydride, olefins, cycloolefins, dienes, alkynes, C5H5-, C7H7+, N-containing heterocycles, aromatics, heteroaromatics, ethers, PF3, phospholes, phosphabenzenes, phosphines (e.g. P(C6I-15)3, P(CH3)(C6I-15)2, P(CH3)2(C6I-15), P(CH3)3, dppe (1,2-ethanediyIbisRdiphenyl)phosphinep, P(C6I-111)3, etc.), phosphinites, phosphonites, phosphites, alkylsulfonates, arylsulfonates, etc.

In particular, in the compounds of the general formula (I), M is selected from PdC12(CNR1), PtC12(CNR1), PdCI(CNR1)2, Au (CNR1) and AuCI, where R1 is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl.
Preferably, R1 is selected from groups of the formulae IV.1 to IV.5, with particular pref-erence given to the formulae IV.1 and IV.2:
#¨C(R)x (IV.1) (Ri)xi (Ri)xi #¨(A)p # ¨(A)p (C1),(2 (IV.2) (IV.3) (R,),0 N¨)( (Ri)x1 #¨(A)p _________________________ (\N¨)C # ¨(A)p N _____________________________ (Cl) N ______ 71((C1),(2 ( (IV.4) IV.5) in which # represents the bonding site to the nitrogen atom, p is 0 or 1, x is 2 or 3, where, in the case that x is 2, the carbon atom which bears the Ri radi-cals additionally bears 1 hydrogen atom, xi in the formulae IV.2, IV.3 and IV.4 is 0, 1, 2, 3, 4, or 5, X2 in the formulae IV.2, IV.3 and IV.4 is 0 or 1, with the proviso that the sum of xi and x2 in the formulae IV.2, IV.3 and IV.4 is 0, 1, 2, 3, 4 or 5, xi in the formula IV.5 is 0, 1 or 2, X2 in the formula IV.5 is 0 or 1, with the proviso that the sum of xi and x2 in the formulae IV.5 is 0, 1 or 2, A where present, is a Ci-Cio-alkylene group which may be interrupted by one or more nonadjacent groups which are selected from -0- and -S-, the IR radicals are each independently selected from Ci-C3o-alkyl, Ci-C3o-alkyloxy or Ci-C30-alkylthio, wherein the alkyl chain in alkyl, alkyloxy or alkylthio may be inter-rupted by one or more nonadjacent oxygen atom(s).
More preferably, in the formulae IV.2, IV.3 and IV.4, xi is 0, 1, 2 or 3, x2 is 0 or 1, with the proviso that the sum of xi and x2 is 0, 1, 2 or 3.
More preferably, R1 is selected from Ci-C6-alkyl, phenyl and phenyl which carries 1, 2 or 3 radicals independently selected from Ci-C6-alkyl and chlorine.
Especially, R1 is selected from isopropyl, tert.-butyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 3,5-dimethylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 3,5-diethylphenyl, 2,6-diethylphenyl, 2,4,6-triethylphenyl, propylphenyl, 3-propylphenyl, 4-propylphenyl, 2,4-dipropylphenyl, 2,5-dipropylphenyl, 3,5-dipropylphenyl, 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-isopropylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 2,4-diisopropylphenyl 2,5-diisopropylphenyl, 3,5-diisopropylphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-butylphenyl, 3-butylphenyl, 4-butylphenyl, 2,4-dibutylphenyl, 2,5-dibutylphenyl, 3,5-dibutylphenyl, 2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-isobutylphenyl, 3-isobutylphenyl, 4-isobutylphenyl, 2,4-diisobutylphenyl, 2,5-diisobutylphenyl, 3,5-diisobutylphenyl, 2,6-diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-sec-butylphenyl, 3-sec-butylphenyl, 4-sec-butylphenyl, 2,4-di-sec-butylphenyl, 2,5-di-sec-butylphenyl, 3,5-di-sec-butylphenyl, 2,6-di-sec-butylphenyl, 2,4,6-tri-sec-butylphenyl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butyl-phenyl, 2,4-di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 3,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, (2-chloro-6-methyl)phenyl, (2-chloro-6-ethyl)phenyl, (2-chloro-6-propyl)phenyl, (2-chloro-6-isopropyl)phenyl, (2-chloro-6-butyl)phenyl, (2-chloro-6-isobutyl)phenyl, (2-chloro-6-sec-butyl)phenyl and (2-chloro-6-tert-butyl)phenyl.
In particular, R1 is selected from tert.-butyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl and (2-chloro-6-methyl)phenyl.
Preferably, R2 is selected from hydrogen, alkyl and cycloalkyl, in particular Ci-C6-alkyl, phenyl-Ci-C6-alkyl and C5-Ci5-cycloalkyl.

More preferably R2 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 1-phenylethyl, cyclopentyl, cyclohexyl, cyclododecyl, cyclopentadecyl and 1-adamantyl.
5 According to a first preferred embodiment, R3 and R4 are independently selected from hydrogen and unsubstituted or substituted aryl. If at least one of the residues R3 and R4 is aryl then this residue is preferably phenyl. In particular, R3 and R4 are both hydrogen.
According to a second preferred embodiment, R3 and R4 together with the carbon atom 10 to which they are bound are 0=0.
According to a third preferred embodiment, R3 is a group 0-R3a, where R3a is a group bound to the oxygen via a carbon atom, silicon atom, sulphur atom, phosphorus, boron or titanium atom. In this embodiment, for compounds of the general formula (I), wherein 15 n is 0, the residues R4 and R7 stand for the bond equivalent of a double bond between the carbon atoms carrying R4 and R7. In this embodiment, for compounds of the gen-eral formula (I), wherein n is 1, the residues R4 and R5 stand for the bond equivalent of a double bond between the carbon atoms carrying R4 and R5.
20 Preferably, R3a is selected from groups of the formulae V-A, V-B, V-C, V-D, V-E, V-F, V-G, V-H, V-I, V-K or V-L, with more preference given to the groups of the formulae V-A, V-B or V-C, wherein RVc vb #¨Si¨RVd #¨S \ #¨S
#¨P¨R' R
,R I Ve 0/ / \ Vh I Vk #/\ RVa # T RVg R R
25 (V-A) (V-B) (V-C) (V-D) (V-E) (V-F) IRVq 0-RVt RVw RI Vm 1\ip I-I- I v V #¨B¨RVr #¨B-0-Rvu #¨Ti¨R, -,B, v ,B, ,R I Vs 1 w + I Vy # R n # 0 R D+ u-R D R
(V-G) (V-H) (V-I) (V-K) (V-L) # represents the bonding site to the oxygen atom, T is selected from -0- and -NRvf, wherein Rvf is hydrogen, alkyl, cycloalkyl or aryl, RVa, RVb, are selected from unsubstituted or substituted alkyl, unsubstituted or substi-tuted cycloalkyl, unsubstituted or substituted aryl and unsubstituted or substituted hetaryl, Rvc, RVd, RVe are independently of each other selected from unsubstituted or sub-stituted alkyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl and unsubstituted or substituted hetaryl, Rvg is selected from unsubstituted or substituted heterocycloalkyl, Rh is selected from unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl and unsubstituted or substituted hetaryl, Rv' and Rvk are independently of each other selected from unsubstituted or substituted alkyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, alkoxy, unsubstituted or substituted aryloxy and unsubstituted or substituted cycloalkyloxy, Rvm and Rvn, are independently of each other selected from unsubstituted or substi-tuted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl and unsubstituted or substituted hetaryl, Rv and RvP, are independently of each other selected from unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl and unsubstituted or substituted hetaryl, Rvq, Rvr and Rvs, are independently of each other selected from unsubstituted or substi-tuted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl and unsubstituted or substituted hetaryl, Rvt, Rvn and Rvv, are independently of each other selected from unsubstituted or substi-tuted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl and unsubstituted or substituted hetaryl, and Rvw, Rvx and Rvv are independently of each other selected from unsubstituted or substi-tuted alkyloxy, unsubstituted or substituted alkenyloxy, unsubstituted or substi-tuted cycloalkyloxy and unsubstituted or substituted aryloxy; and D+ is a cation equivalent.
The cation equivalent D+ serves merely as counterion and can be selected freely from among monovalent cations and the parts of polyvalent cations corresponding to a sin-gle positive charge. Suitable cations are, for example, alkali metal ions D+, e.g. Na + and K+, earth alkali metal cations, e.g. Ca2+, ammonium ions.

Preferably, Rva is phenyl, which is unsubstituted or substituted by 1, 2 or 3 radicals independently selected from C1-G4-alkyl, Ci-C4alkoxy and nitro.
Preferably, Rvb is (Ci-C4alkyl)phenyl, wherein the phenyl moiety of (Ci-C4alkyl)phenyl is unsubstituted or substituted by 1, 2 or 3 radicals independently selected from Ci-C4-alkyl, Ci-C4alkoxy and nitro.
Preferably T is -0-. In the radical of the formula V-B, T is preferably -0-and Rvb is ben-zyl wherein the phenyl moiety of benzyl is unsubstituted or substituted by 1, 2 or 3 radi-cals independently selected from Ci-C4alkyl, Ci-C4alkoxy and nitro.
Preferably, Rvc, Rvd and Rve are independently of each other selected from Ci-C6-alkyl, C5-Cio-cycloalkyl and phenyl which is unsubstituted or substituted by 1, 2 or 3 radicals independently selected from Ci-C4alkyl and Ci-C4alkoxy. Examples for a radical V-C
are trimethylsilyl, triethylsilyl, triisopropylsilyl, dimethylisopropylsilyl, diethylisopropyl-silyl, dimethylhexylsilyl, 2-norbornyldimethylsilyl, tert-butyldimethylsilyl, di-tert-butylmethylsilyl, tert-butyldiphenylsilyl, tribenzylsilyl, triphenylsilyl and diphenylmethyl-silyl.
Preferably, the radical of the formula V-D is 2,2,5,5-tetramethylpyrrolidin-3-one-1-sulfinate.
Preferably, Rvb is Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkyl substituted by phenyl wherein phenyl is unsubstituted or substituted by 1, 2 or 3 radicals independently se-lected from Ci-C4alkyl, Ci-C4alkoxy, Ci-C4haloalkyl, Ci-C4haloalkoxy and nitro, C2' C6-alkenyl, benzyl, phenyl, wherein phenyl is unsubstituted or substituted by 1, 2 or 3 radicals independently selected from Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4haloalkoxy, Ci-C4alkoxy and nitro. Examples of radicals of the formula V-E are methanesulfonate, trifluoromethanesulfonate, 2-[(4-nitrophenypethyl]sulfonate, allylsulfonate, benzylsul-fonate, tosylate, and 2-trifluoromethylbenzenesulfonate.
Preferably, Rv' and Rvk are independently of each other selected from Ci-C6-alkyl, Ci-C6-alkoxy and phenyl, which is unsubstituted or substituted by 1, 2 or 3 radicals inde-pendently selected from Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4haloalkoxy and Ci-C4-alkoxy.
Preferably, R7, R8, and, if present, R5 and R6 are independently selected from hydrogen and unsubstituted or substituted aryl. If at least one of the residues R7, R8, and, if pre-sent, R5 and R6 is aryl then this residue is preferably phenyl. In a first preferred em-bodiment, R7, R8, and, if present, R5 and R6 are all hydrogen. In a second preferred embodiment, one of the residues, selected from R7, R8, and, if present, R5 and R6 is phenyl and the other residues are all hydrogen.
In a special embodiment, the two radicals R2 and R8 may also form together with the N
atom to which R2 and the carbon atom to which R8 are bound a 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11- or12-membered, unsubstituted or substituted nitrogen heterocycle which may optionally have 1, 2 or 3 further heteroatoms or heteroatom containing groups inde-pendently selected from 0, N, N Ra and S as ring members, wherein Ra is hydrogen, alkyl, cycloalkyl or aryl. Suitable substituents on the 3- to 12-membered nitrogen het-erocycle are preferably halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-Cs-alkyl, Ci-C6-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-C6-haloalkoxy, and Ci-C6-alkylthio and/ or two substituents that are bound to adjacent atoms of the 3- to 12-membered heterocycle form together with said atoms a fused benzene ring, a fused naphthalene ring, a fused saturated or partially unsaturated 5-, 6-, or 7-membered car-bocycle or a fused 5-, 6-, or 7-membered heterocycle, which contains 1, 2, 3 or 4 het-eroatoms selected from oxygen, sulfur and NRa, wherein Ra is as defined above, as ring members, and wherein the fused ring is unsubstituted or may carry any combina-tion of 1, 2, 3, or 4 radicals selected from halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-C6-alkyl, Ci-C6-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-C6-haloalkoxy, and Ci-C6-alkylthio.
Preferred are compounds of the general formula (1-D) 0,5 R4 Fµ
n M
(I-D) where n, M, R1, R3, R4, R5 and R6 have the aforementioned meanings, in particular the meanings mentioned as preferred. In particular, n is 0, M is selected from PdC12(CNR1), PdCI(CNR1) 2, PtC12(CNR1), Au(CNR1) and AuCI, R1 is selected from tert.-butyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl and (2-chloro-6-methyl)phenyl, and R3 and R4 are both hydrogen.
In the aforementioned first variant, the process of the invention is employed for prepar-ing compounds of the formula (1-A.1) or (1-A.2) M M
(I-A.1) (I-A.2) where M, R1, R2, R5, R6, R7 and R8 have the aforementioned meanings, in particular the meanings mentioned as preferred, R3 and R4 are independently selected from hydrogen and in each case unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dialkyl)amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl)amino, (dicycloalkyl)amino, hetero-cycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl)amino, (diheterocycloalkyl)amino, aryl, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl)amino and (dihetaryl)amino.
In a preferred embodiment of the first variant, the process of the invention is employed for preparing compounds of the general formula (I-A.2.1) R) R7 N-----n2 RiN./ rµ
M
(I-A.2.1) where M, R1, R2, R3 and R7 have the aforementioned meanings, in particular the meanings mentioned as preferred.
(In the formula I-A.2.1 the residues R4 and R8 are hydrogen and are not depicted.) The compounds of the general formula (I-A.2.2) which are indicated in Tables 1 to 5 below represent per se preferred embodiments of the present invention. The meanings for R1, R2 and R3 indicated in Table A below represent embodiments of the invention which are likewise preferred independently of one another and especially in combina-tion.

R) \
(1-A.2.2) Ri R
M
Table 1 Compounds of the formula (1-A.2.2) in which the group M is PdC12(CNR1) and the com-bination of R1, R2 and R3 for a compound in each case corresponds to one line of Ta-5 ble A. The residue R1 bound to the ring nitrogen atom and the residue R1 in the group PdC12(CNR1) have both the same meaning. In comparison to the general formula (I), in formula (1-A.2.2) n is 0 and the residues R4, R7 and R8 are hydrogen and are not de-picted.
10 Table 2 Compounds of the formula (1-A.2.2) in which the group M is PtC12(CNR1) and the com-bination of R1, R2 and R3 for a compound in each case corresponds to one line of Ta-ble A. The residue R1 bound to the ring nitrogen atom and the residue R1 in the group PtC12(CNR1) have both the same meaning.
Table 3 Compounds of the formula (1-A.2.2) in which the group M is PdC1(CNR1)2 and the com-bination of R1, R2 and R3 for a compound in each case corresponds to one line of Ta-ble A. The residue R1 bound to the ring nitrogen atom and the residue R1 in the group PdC1(CNR1)2 have both the same meaning.
Table 4 Compounds of the formula (1-A.2.2) in which the group M is AuCI and the combination of R1, R2 and R3 for a compound in each case corresponds to one line of Table A.
Table 5 Compounds of the formula (1-A.2.2) in which the group M is Au(CNR1) and the combi-nation of R1, R2 and R3 for a compound in each case corresponds to one line of Ta-ble A. The residue R1 bound to the ring nitrogen atom and the residue R1 in the group AuCI(CNR1) have both the same meaning.
Table A
No. R1 R2 R3 A-1 2,6-dimethyl phenyl methyl H
A-2 2,6-dimethyl phenyl ethyl H

No. R1 R2 R3 A-3 2,6-dimethylphenyl n-propyl H
A-4 2,6-dimethylphenyl isopropyl H
A-5 2,6-dimethylphenyl butyl H
A-6 2,6-dimethylphenyl isobutyl H
A-7 2,6-dimethylphenyl sec-buty H
A-8 2,6-dimethylphenyl tert-butyl H
A-9 2,6-dimethylphenyl cyclohexyl H
A-10 2,6-dimethylphenyl 1-adamantyl H
A-11 2,6-dimethylphenyl methyl phenyl A-12 2,6-dimethylphenyl ethyl phenyl A-13 2,6-dimethylphenyl n-propyl phenyl A-14 2,6-dimethylphenyl isopropyl phenyl A-15 2,6-dimethylphenyl butyl phenyl A-16 2,6-dimethylphenyl isobutyl phenyl A-17 2,6-dimethylphenyl sec-buty phenyl A-18 2,6-dimethylphenyl tert-butyl phenyl A-19 2,6-dimethylphenyl cyclohexyl phenyl A-20 2,6-dimethylphenyl 1-adamantyl phenyl A-21 2,4,6-trimethylphenyl methyl H
A-22 2,4,6-trimethylphenyl ethyl H
A-23 2,4,6-trimethylphenyl n-propyl H
A-24 2,4,6-trimethylphenyl isopropyl H
A-25 2,4,6-trimethylphenyl butyl H
A-26 2,4,6-trimethylphenyl isobutyl H
A-27 2,4,6-trimethylphenyl sec-buty H
A-28 2,4,6-trimethylphenyl tert-butyl H
A-29 2,4,6-trimethylphenyl cyclohexyl H
A-30 2,4,6-trimethylphenyl 1-adamantyl H
A-31 2,4,6-trimethylphenyl methyl phenyl A-32 2,4,6-trimethylphenyl ethyl phenyl A-33 2,4,6-trimethylphenyl n-propyl phenyl A-34 2,4,6-trimethylphenyl isopropyl phenyl A-35 2,4,6-trimethylphenyl n-butyl phenyl A-36 2,4,6-trimethylphenyl isobutyl phenyl A-37 2,4,6-trimethylphenyl sec-buty phenyl A-38 2,4,6-trimethylphenyl tert-butyl phenyl A-39 2,4,6-trimethylphenyl cyclohexyl phenyl No. R1 R2 R3 A-40 2,4,6-trimethylphenyl 1-adamantyl phenyl A-41 2,6-diisopropylphenyl methyl H
A-42 2,6-diisopropylphenyl ethyl H
A-43 2,6-diisopropylphenyl n-propyl H
A-44 2,6-diisopropylphenyl isopropyl H
A-45 2,6-diisopropylphenyl n-butyl H
A-46 2,6-diisopropylphenyl isobutyl H
A-47 2,6-diisopropylphenyl sec-buty H
A-48 2,6-diisopropylphenyl tert-butyl H
A-49 2,6-diisopropylphenyl cyclohexyl H
A-50 2,6-diisopropylphenyl 1-adamantyl H
A-51 2,6-diisopropylphenyl methyl phenyl A-52 2,6-diisopropylphenyl ethyl phenyl A-53 2,6-diisopropylphenyl n-propyl phenyl A-54 2,6-diisopropylphenyl isopropyl phenyl A-55 2,6-diisopropylphenyl n-butyl phenyl A-56 2,6-diisopropylphenyl isobutyl phenyl A-57 2,6-diisopropylphenyl sec-buty phenyl A-58 2,6-diisopropylphenyl tert-butyl phenyl A-59 2,6-diisopropylphenyl cyclohexyl phenyl A-60 2,6-diisopropylphenyl 1-adamantyl phenyl A-61 (2-chloro-6-methyl)phenyl methyl H
A-62 (2-chloro-6-methyl)phenyl ethyl H
A-63 (2-chloro-6-methyl)phenyl n-propyl H
A-64 (2-chloro-6-methyl)phenyl isopropyl H
A-65 (2-chloro-6-methyl)phenyl n-butyl H
A-66 (2-chloro-6-methyl)phenyl isobutyl H
A-67 (2-chloro-6-methyl)phenyl sec-buty H
A-68 (2-chloro-6-methyl)phenyl tert-butyl H
A-69 (2-chloro-6-methyl)phenyl cyclohexyl H
A-70 (2-chloro-6-methyl)phenyl 1-adamantyl H
A-71 (2-chloro-6-methyl)phenyl methyl phenyl A-72 (2-chloro-6-methyl)phenyl ethyl phenyl A-73 (2-chloro-6-methyl)phenyl n-propyl phenyl A-74 (2-chloro-6-methyl)phenyl isopropyl phenyl A-75 (2-chloro-6-methyl)phenyl n-butyl phenyl A-76 (2-chloro-6-methyl)phenyl isobutyl phenyl No. R1 R2 R3 A-77 (2-chloro-6-methyl)phenyl sec-buty phenyl A-78 (2-chloro-6-methyl)phenyl tert-butyl phenyl A-79 (2-chloro-6-methyl)phenyl cyclohexyl phenyl A-80 (2-chloro-6-methyl)phenyl 1-adamantyl phenyl A-81 tert-butyl methyl H
A-82 tert-butyl ethyl H
A-83 tert-butyl n-propyl H
A-84 tert-butyl isopropyl H
A-85 tert-butyl n-butyl H
A-86 tert-butyl isobutyl H
A-87 tert-butyl sec-buty H
A-88 tert-butyl tert-butyl H
A-89 tert-butyl cyclohexyl H
A-90 tert-butyl 1-adamantyl H
A-91 tert-butyl methyl phenyl A-92 tert-butyl ethyl phenyl A-93 tert-butyl n-propyl phenyl A-94 tert-butyl isopropyl phenyl A-95 tert-butyl n-butyl phenyl A-96 tert-butyl isobutyl phenyl A-97 tert-butyl sec-buty phenyl A-98 tert-butyl tert-butyl phenyl A-99 tert-butyl cyclohexyl phenyl A-100 tert-butyl 1-adamantyl phenyl In a preferred embodiment of the aforementioned second variant, the process of the invention is employed for preparing compounds of the general formula (I-B.1) or (I-B.2) 0 R C) \R
1 \

R1N/N'R2 R
M M
(I-B.1) (I-B.2) where M, R1, R2, R5, R6, R7 and R8 have the aforementioned meanings, in particular the meanings mentioned as preferred.
In an especially preferred embodiment of the second variant, the process of the inven-tion is employed for preparing compounds of the general formula (1-B.2.1) ________________________________ \
N----m2 RiNz rx (I-B.2.1) M
where M, R1 and R2 have the aforementioned meanings, in particular the meanings men-tioned as preferred.
The compounds of the general formula (1-B.2.1) which are indicated in Tables 6 to 10 below represent per se preferred embodiments of the present invention. The meanings for R1 and R2 indicated in Table B below represent embodiments of the invention which are likewise preferred independently of one another and especially in combination.
Table 6 Compounds of the formula (1-B.2.1) in which the group M is PdC12(CNR1) and the com-bination of R1 and R2 for a compound in each case corresponds to one line of Table B.
The residue R1 bound to the ring nitrogen atom and the residue R1 in the group PdC12(CNR1) have both the same meaning. In comparison to the general formula (I), in formula (1-B.2.1) n is 0 and the residues R7 and R8 are hydrogen and are not depicted.
Table 7 Compounds of the formula (1-B.2.1) in which the group M is PtC12(CNR1) and the com-bination of R1 and R2 for a compound in each case corresponds to one line of Table B.
The residue R1 bound to the ring nitrogen atom and the residue R1 in the group PtC12(CNR1) have both the same meaning.
Table 8 Compounds of the formula (1-B.2.1) in which the group M is PdCI(CNR1)2 and the com-bination of R1, R2 and R3 for a compound in each case corresponds to one line of Ta-ble B. The residue R1 bound to the ring nitrogen atom and the residue R1 in the group PdCI (CNR1) 2 have both the same meaning.

Table 9 Compounds of the formula (I-B.2.1) in which the group M is AuCI and the combination of R1 and R2 for a compound in each case corresponds to one line of Table B.
5 Table 10 Compounds of the formula (I-B.2.1) in which the group M is Au(CNR1) and the combi-nation of R1 and R2 for a compound in each case corresponds to one line of Table B.
The residue R1 bound to the ring nitrogen atom and the residue R1 in the group AuCI(CNR1) have both the same meaning.
Table B
No. R1 R2 B-1 2,6-dimethylphenyl isopropyl B-2 2,6-dimethylphenyl tert-butyl B-3 2,6-dimethylphenyl cyclohexyl B-4 2,6-dimethylphenyl cyclododecyl B-5 2,6-dimethylphenyl 1-adamantyl B-6 2,6-dimethylphenyl 1-phenylethyl B-7 2,4,6-trimethylphenyl isopropyl B-8 2,4,6-trimethylphenyl tert-butyl B-9 2,4,6-trimethylphenyl cyclohexyl B-10 2,4,6-trimethylphenyl cyclododecyl B-11 2,4,6-trimethylphenyl 1-adamantyl B-12 2,4,6-trimethylphenyl 1-phenylethyl B-13 2,6-diisopropylphenyl isopropyl B-14 2,6-diisopropylphenyl tert-butyl B-15 2,6-diisopropylphenyl cyclohexyl B-16 2,6-diisopropylphenyl cyclododecyl B-17 2,6-diisopropylphenyl 1-adamantyl B-18 2,6-diisopropylphenyl 1-phenylethyl B-19 (2-chloro-6-methyl)phenyl isopropyl B-20 (2-chloro-6-methyl)phenyl tert-butyl B-21 (2-chloro-6-methyl)phenyl cyclohexyl B-22 (2-chloro-6-methyl)phenyl cyclododecyl B-23 (2-chloro-6-methyl)phenyl 1-adamantyl B-24 (2-chloro-6-methyl)phenyl 1-phenylethyl B-25 tert-butyl isopropyl B-26 tert-butyl tert-butyl No. R1 R2 B-27 tert-butyl cyclohexyl B-28 tert-butyl cyclododecyl B-29 tert-butyl 1-adamantyl B-30 tert-butyl 1-phenylethyl In a preferred embodiment of the third variant, the process of the invention is employed for preparing compounds of the general formula (I-0.1) or (I-C.2) 3a ,-,3a R ¨0)_(R
R ¨V7 R1NzN'R2 M M
(1-0.1) (1-0.2) where M, R1, R2, R3a, R6, R7 and R8 have the aforementioned meanings, in particular the meanings mentioned as preferred.
In an especially preferred embodiment of the third variant, the process of the invention is employed for preparing compounds of the general formula (I-0.2.1) R3a¨O
)_ _______________________________________ \
M
(I-0.2.1) where M, R1, R2 and R3a have the aforementioned meanings, in particular the meanings men-tioned as preferred.
The compounds of the general formula (I-0.2.1) which are indicated in Tables 11 to 15 below represent per se preferred embodiments of the present invention. The meanings for R1, R2 and R3a indicated in Table C below represent embodiments of the invention which are likewise preferred independently of one another and especially in combina-tion.

Table 10 Compounds of the formula (1-C.2.1) in which the group M is PdC12(CNR1) and the com-bination of R1, R2 and R3a for a compound in each case corresponds to one line of Ta-ble C. The residue R1 bound to the ring nitrogen atom and the residue R1 in the group PdC12(CNR1) have both the same meaning. In comparison to the general formula (I), in formula (1-C.2.1) n is 0 and the residue R8 is hydrogen and is not depicted.
Table 11 Compounds of the formula (1-C.2.1) in which the group M is PtC12(CNR1) and the com-bination of R1, R2 and R3a for a compound in each case corresponds to one line of Ta-ble C. The residue R1 bound to the ring nitrogen atom and the residue R1 in the group PtC12(CNR1) have both the same meaning.
Table 12 Compounds of the formula (1-C.2.1) in which the group M is PdCI(CNR1)2 and the com-bination of R1, R2 and R3 for a compound in each case corresponds to one line of Ta-ble C. The residue R1 bound to the ring nitrogen atom and the residue R1 in the group PdCI(CNR1)2 have both the same meaning.
Table 14 Compounds of the formula (1-C.2.1) in which the group M is AuCI and the combination of R1, R2 and R3a for a compound in each case corresponds to one line of Table C.
Table 15 Compounds of the formula (1-C.2.1) in which the group M is Au(CNR1) and the combi-nation of R1, R2 and R3a for a compound in each case corresponds to one line of Ta-ble C. The residue R1 bound to the ring nitrogen atom and the residue R1 in the group Au(CNR1) have both the same meaning.
Table C
No. R1 R2 R3a C-1 2,6-dimethyl phenyl isopropyl tert-butyldiphenylsilyl C-2 2 ,6-d imethylphenyl tert-butyl tert-butyldiphenylsilyl C-3 2 ,6-dimethyl phenyl cyclohexyl tert-butyldiphenylsilyl C-4 2 ,6-d imethylphenyl cyclododecyl tert-butyldiphenylsilyl C-5 2,6-d imethylphenyl 1-adamantyl tert-butyldiphenylsilyl C-6 2 ,6-d imethylphenyl 1-phenylethyl tert-butyldiphenylsilyl C-7 2 ,6-dimethyl phenyl isopropyl benzoyl No. R1 R2 R3a 0-8 2,6-dimethylphenyl tert-butyl benzoyl 0-9 2,6-dimethylphenyl cyclohexyl benzoyl C-10 2,6-dimethylphenyl cyclododecyl benzoyl C-11 2,6-dimethylphenyl 1-adamantyl benzoyl C-12 2,6-dimethylphenyl 1-phenylethyl benzoyl C-13 2,6-dimethylphenyl isopropyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl C-14 2,6-dimethylphenyl tert-butyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl C-15 2,6-dimethylphenyl cyclohexyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl C-16 2,6-dimethylphenyl cyclododecyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl C-17 2,6-dimethylphenyl 1-adamantyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl C-18 2,6-dimethylphenyl 1-phenylethyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl C-19 2,6-diisopropylphenyl isopropyl tert-butyldiphenylsilyl 0-20 2,6-diisopropylphenyl tert-butyl tert-butyldiphenylsilyl 0-21 2,6-diisopropylphenyl cyclohexyl tert-butyldiphenylsilyl 0-22 2,6-diisopropylphenyl cyclododecyl tert-butyldiphenylsilyl 0-23 2,6-diisopropylphenyl 1-adamantyl tert-butyldiphenylsilyl 0-24 2,6-diisopropylphenyl 1-phenylethyl tert-butyldiphenylsilyl 0-25 2,6-diisopropylphenyl isopropyl benzoyl 0-26 2,6-diisopropylphenyl tert-butyl benzoyl 0-27 2,6-diisopropylphenyl cyclohexyl benzoyl 0-28 2,6-diisopropylphenyl cyclododecyl benzoyl 0-29 2,6-diisopropylphenyl 1-adamantyl benzoyl 0-30 2,6-diisopropylphenyl 1-phenylethyl benzoyl 0-31 2,6-diisopropylphenyl isopropyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl 0-32 2,6-diisopropylphenyl tert-butyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl 0-33 2,6-diisopropylphenyl cyclohexyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl 0-34 2,6-diisopropylphenyl cyclododecyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl No. R1 R2 R3a 0-35 2,6-diisopropylphenyl 1-adamantyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl 0-36 2,6-diisopropylphenyl 1-phenylethyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl 0-37 (2-chloro-6-methyl)phenyl isopropyl tert-butyldiphenylsilyl 0-38 (2-chloro-6-methyl)phenyl tert-butyl tert-butyldiphenylsilyl 0-39 (2-chloro-6-methyl)phenyl cyclohexyl tert-butyldiphenylsilyl 0-40 (2-chloro-6-methyl)phenyl cyclododecyl tert-butyldiphenylsilyl C-41 (2-chloro-6-methyl)phenyl 1-adamantyl tert-butyldiphenylsilyl 0-42 (2-chloro-6-methyl)phenyl 1-phenylethyl tert-butyldiphenylsilyl 0-43 (2-chloro-6-methyl)phenyl isopropyl benzoyl 0-44 (2-chloro-6-methyl)phenyl tert-butyl benzoyl 0-45 (2-chloro-6-methyl)phenyl cyclohexyl benzoyl 0-46 (2-chloro-6-methyl)phenyl cyclododecyl benzoyl 0-47 (2-chloro-6-methyl)phenyl 1-adamantyl benzoyl 0-48 (2-chloro-6-methyl)phenyl 1-phenylethyl benzoyl 0-49 (2-chloro-6-methyl)phenyl isopropyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl 0-50 (2-chloro-6-methyl)phenyl tert-butyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl C-51 (2-chloro-6-methyl)phenyl cyclohexyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl 0-52 (2-chloro-6-methyl)phenyl cyclododecyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl 0-53 (2-chloro-6-methyl)phenyl 1-adamantyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl 0-54 (2-chloro-6-methyl)phenyl 1-phenylethyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl 0-55 tert-butyl isopropyl tert-butyldiphenylsilyl 0-56 tert-butyl tert-butyl tert-butyldiphenylsilyl 0-57 tert-butyl cyclohexyl tert-butyldiphenylsilyl 0-58 tert-butyl cyclododecyl tert-butyldiphenylsilyl 0-59 tert-butyl 1-adamantyl tert-butyldiphenylsilyl 0-60 tert-butyl 1-phenylethyl tert-butyldiphenylsilyl 0-61 tert-butyl isopropyl benzoyl 0-62 tert-butyl tert-butyl benzoyl 0-63 tert-butyl cyclohexyl benzoyl No. R1 R2 R3a 0-64 tert-butyl cyclododecyl benzoyl 0-65 tert-butyl 1-adamantyl benzoyl 0-66 tert-butyl 1-phenylethyl benzoyl 0-67 tert-butyl isopropyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl 0-68 tert-butyl tert-butyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl 0-69 tert-butyl cyclohexyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl 0-70 tert-butyl cyclododecyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl 0-71 tert-butyl 1-adamantyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl 0-72 tert-butyl 1-phenylethyl 4,5-dimethoxy-2-nitrobenzyloxycarbonyl In a preferred embodiment of the second aspect, the process of the invention is em-ployed for preparing compounds of the general formula I-E, R3\
/ (R8 RiN N¨R2 (I-E) M

where M, R1, R2, R3 and R8 have the aforementioned meanings. In this embodiment, R1 and R2 have preferably different meanings.
R1 is preferably selected from groups of the formulae IV.1 to IV.5, with particular pref-erence given to the formulae IV.1 and IV.2. More preferably, R1 is selected from 01-06-alkyl, phenyl and phenyl which carries 1, 2 or 3 radicals independently selected from 01-06-alkyl and chlorine. In particular preferably, R1 is selected from tert.-butyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl and (2-chloro-6-methyl)phenyl.
Preferably, R2 is selected from alkyl and cycloalkyl, in particular 01-06-alkyl, phenyl-Ci-06-alkyl and 05-015-cycloalkyl. In particular, R2 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, cyclopentyl, cyclohexyl, cyclododecyl and 1-adamantyl.
Preferably, R3 is selected from hydrogen, alkyl, cycloalkyl and aryl, more preferably hydrogen, C1-C6-alkyl and C6-C10-aryl.
Preferably, R8 is selected from hydrogen, alkyl, cycloalkyl and aryl, more preferably hydrogen, Ci-C6-alkyl and C6-C10-aryl.
M is preferably selected from PdC12(CNR1), PtC12(CNR1), PdCI(CNR1)2, Au (CNR1) and AuCI, where R1 is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl.
In an especially preferred embodiment of the second aspect, the process of the inven-tion is employed for preparing compounds of the formula I-E.1, Ú¨\ 2 N (I-E.1) M
where M, R1 and R2 have the aforementioned meanings, in particular the meanings mentioned as preferred.
The compounds of the general formula (1-E.1) which are indicated in Tables 16 to 20 below represent per se preferred embodiments of the present invention. The meanings for R1 and R2 indicated in Table D below represent embodiments of the invention which are likewise preferred independently of one another and especially in combination.
Table 16 Compounds of the formula (1-E.1) in which the group M is PdC12(CNR1) and the combi-nation of R1 and R2 for a compound in each case corresponds to one line of Table D.
The residue R1 bound to the ring nitrogen atom and the residue R1 in the group PdC12(CNR1) have both the same meaning.
Table 17 Compounds of the formula (1-E.1) in which the group M is PtC12(CNR1) and the combi-nation of R1 andR2 for a compound in each case corresponds to one line of Table D.
The residue R1 bound to the ring nitrogen atom and the residue R1 in the group PtC12(CNR1) have both the same meaning.

Table 18 Compounds of the formula (I-E.1) in which the group M is PdCI(CNR1)2 and the combi-nation of R1 andR2 for a compound in each case corresponds to one line of Table D.
The residue R1 bound to the ring nitrogen atom and the residue R1 in the group PdCI(CNR1) 2 have both the same meaning.
Table 19 Compounds of the formula (I-E.1) in which the group M is AuCI and the combination of R1 andR2 for a compound in each case corresponds to one line of Table D.
Table 20 Compounds of the formula (I-E.1) in which the group M is Au(CNR1) and the combina-tion of R1 andR2 for a compound in each case corresponds to one line of Table D. he residue R1 bound to the ring nitrogen atom and the residue R1 in the group Au(CNR1) have both the same meaning.
Table D
No. R1 R2 D-1 2,6-dimethylphenyl isopropyl D-2 2,6-dimethylphenyl tert-butyl D-3 2,6-dimethylphenyl cyclohexyl D-4 2,6-dimethylphenyl cyclododecyl D-5 2,6-dimethylphenyl 1-adamantyl D-6 2,6-dimethylphenyl 1-phenylethyl D-7 2,4,6-trimethylphenyl isopropyl D-8 2,4,6-trimethylphenyl tert-butyl D-9 2,4,6-trimethylphenyl cyclohexyl D-10 2,4,6-trimethylphenyl cyclododecyl D-11 2,4,6-trimethylphenyl 1-adamantyl D-12 2,4,6-trimethylphenyl 1-phenylethyl D-13 2,6-diisopropylphenyl isopropyl D-14 2,6-diisopropylphenyl tert-butyl D-15 2,6-diisopropylphenyl cyclohexyl D-16 2,6-diisopropylphenyl cyclododecyl D-17 2,6-diisopropylphenyl 1-adamantyl D-18 2,6-diisopropylphenyl 1-phenylethyl D-19 (2-chloro-6-methyl)phenyl isopropyl D-20 (2-chloro-6-methyl)phenyl tert-butyl D-21 (2-chloro-6-methyl)phenyl cyclohexyl No. R1 R2 D-22 (2-chloro-6-methyl)phenyl cyclododecyl D-23 (2-chloro-6-methyl)phenyl 1-adamantyl D-24 (2-chloro-6-methyl)phenyl 1-phenylethyl D-25 tert-butyl isopropyl D-26 tert-butyl tert-butyl D-27 tert-butyl cyclohexyl D-28 tert-butyl cyclododecyl D-29 tert-butyl 1-adamantyl D-30 tert-butyl 1-phenylethyl In a preferred embodiment of the third aspect, the process according to the invention is employed for preparing compounds of the general formula I-F
EWG _____________________________________ i 4 R87 R
RiN yN'R2 (I-F) ¨
M
where M, EWG, R1, R2, R4, R7 and R8 have the aforementioned meanings. In this embodi-ment, R1 and R2 have preferably different meanings.
In this embodiment, R1 is preferably selected from phenyl, naphthyl, phenyl which car-ries 1, 2 or 3 radicals independently selected from C1-C8-alkyl and Ci-Cs-haloalkyl, and naphthyl which carries 1, 2 or 3 radicals independently selected from Ci-Cs-alkyl and Ci-Cs-haloalkyl, in particular Ci-Cs-alkyl or Ci-Cs-fluoroalkyl. Especially R1 is selected from 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, 2-trifluoromethylphenyl, 2,6-di-(trifluoromethyl)phenyl, 1-napthyl and 2-naphthyl.
Preferably, R2 is selected from alkyl and cycloalkyl, in particular Ci-Cs-alkyl, phenyl-Ci-Cs-alkyl and Cs-Cis-cycloalkyl. More preferably, R2 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 1-phenylethyl, cyclopentyl, cyclohexyl, cyclododecyl and 1-adamantyl.
Preferably, R4 is selected from hydrogen, alkyl, cycloalkyl and aryl, more preferably hydrogen and Ci-Cio-alkyl.

Preferably, R7 and R8 are independently of each other selected from hydrogen, alkyl, cycloalkyl and aryl, more preferably hydrogen and Ci-Cio-alkyl.
EWG is preferably C(0)R14 or C(0)0R14, especially C(0)0R14. In this embodiment is preferably Ci-C6-alkyl, especially Ci-C4-alkyl swuch as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
M is preferably selected from PdC12(CNR1), PtC12(CNR1), PdCI(CNR1)2, Au (CNR1) and AuCI, where R1 is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl.
Preference is given to compounds of formula 1-F.1, EWGTh \
Ri N R
N¨ 2 (I-F.1) M
where EWG, M, R1 and R2 have the aforementioned meanings, preferably those being preferred.
The compounds of the general formula (1-F.1) which are indicated in Tables 21 to 30 below represent per se preferred embodiments of the present invention. The meanings for R1 and R2 indicated in Table E below represent embodiments of the invention which are likewise preferred independently of one another and especially in combination.
Table 21 Compounds of the formula (1-F.1) in which the group M is PdC12(CNR1), EWG is meth-oxycarbonyl and the combination of R1 and R2 for a compound in each case corre-sponds to one line of Table E. The residue R1 bound to the ring nitrogen atom and the residue R1 in the group PdC12(CNR1) have both the same meaning.
Table 22 Compounds of the formula (1-F.1) in which the group M is PtC12(CNR1), EWG is meth-oxycarbonyl and the combination of R1 andR2 for a compound in each case corre-sponds to one line of Table E. The residue R1 bound to the ring nitrogen atom and the residue R1 in the group PtC12(CNR1) have both the same meaning.
Table 23 Compounds of the formula (1-F.1) in which the group M is PdCI(CNR1)2, EWG is meth-oxycarbonyl and the combination of R1 andR2 for a compound in each case corre-sponds to one line of Table E. The residue R1 bound to the ring nitrogen atom and the residue R1 in the group PdCI(CNR1) 2 have both the same meaning.

Table 24 Compounds of the formula (1-F.1) in which the group M is AuCI, EWG is methoxycar-bonyl and the combination of R1 andR2 for a compound in each case corresponds to one line of Table E.
Table 25 Compounds of the formula (1-F.1) in which the group M is Au(CNR1), EWG is methoxy-carbonyl and the combination of R1 andR2 for a compound in each case corresponds to one line of Table E. he residue R1 bound to the ring nitrogen atom and the residue R1 in the group Au(CNR1) have both the same meaning.
Table 26 Compounds of the formula (1-F.1) in which the group M is PdC12(CNR1), EWG is eth-oxycarbonyl and the combination of R1 and R2 for a compound in each case corre-sponds to one line of Table E. The residue R1 bound to the ring nitrogen atom and the residue R1 in the group PdC12(CNR1) have both the same meaning.
Table 27 Compounds of the formula (1-F.1) in which the group M is PtC12(CNR1), EWG is eth-oxycarbonyl and the combination of R1 andR2 for a compound in each case corre-sponds to one line of Table E. The residue R1 bound to the ring nitrogen atom and the residue R1 in the group PtC12(CNR1) have both the same meaning.
Table 28 Compounds of the formula (1-F.1) in which the group M is PdCI(CNR1)2, EWG is eth-oxycarbonyl and the combination of R1 andR2 for a compound in each case corre-sponds to one line of Table E. The residue R1 bound to the ring nitrogen atom and the residue R1 in the group PdCI(CNR1) 2 have both the same meaning.
Table 29 Compounds of the formula (1-F.1) in which the group M is AuCI, EWG is ethoxycar-bonyl and the combination of R1 andR2 for a compound in each case corresponds to one line of Table E.

Table 30 Compounds of the formula (l-F.1) in which the group M is Au(CNR1), EWG is ethoxy-carbonyl and the combination of R1 andR2 for a compound in each case corresponds to one line of Table E. he residue R1 bound to the ring nitrogen atom and the residue R1 in the group Au(CNR1) have both the same meaning.
Table E
No. R1 R2 E-1 2,6-dimethylphenyl isopropyl E-2 2,6-dimethylphenyl tert-butyl E-3 2,6-dimethylphenyl cyclohexyl E-4 2,6-dimethylphenyl cyclododecyl E-5 2,6-dimethylphenyl 1-adamantyl E-6 2,6-dimethylphenyl 1-phenylethyl E-7 2,4,6-trimethylphenyl isopropyl E-8 2,4,6-trimethylphenyl tert-butyl E-9 2,4,6-trimethylphenyl cyclohexyl E-10 2,4,6-trimethylphenyl cyclododecyl E-11 2,4,6-trimethylphenyl 1-adamantyl E-12 2,4,6-trimethylphenyl 1-phenylethyl E-13 2,6-diisopropylphenyl isopropyl E-14 2,6-diisopropylphenyl tert-butyl E-15 2,6-diisopropylphenyl cyclohexyl E-16 2,6-diisopropylphenyl cyclododecyl E-17 2,6-diisopropylphenyl 1-adamantyl E-18 2,6-diisopropylphenyl 1-phenylethyl E-19 (2-trifluromethyl)phenyl isopropyl E-20 (2-trifluromethyl)phenyl tert-butyl E-21 (2-trifluromethyl)phenyl cyclohexyl E-22 (2-trifluromethyl)phenyl cyclododecyl E-23 (2-trifluromethyl)phenyl 1-adamantyl E-24 (2-trifluromethyl)phenyl 1-phenylethyl E-25 1-naphthyl isopropyl E-26 1-naphthyl tert-butyl E-27 1-naphthyl cyclohexyl E-28 1-naphthyl cyclododecyl E-29 1-naphthyl 1-adamantyl E-30 1-naphthyl 1-phenylethyl No. R1 R2 E-31 2-naphthyl isopropyl E-32 2-naphthyl tert-butyl E-33 2-naphthyl cyclohexyl E-34 2-naphthyl cyclododecyl E-35 2-naphthyl 1-adamantyl E-36 2-naphthyl 1-phenylethyl Step al) In step al) of the process according to the invention an isonitrile complex of the gen-eral formula (II) R1-NEC-M is employed, wherein R1 and M have one of the meanings given above.
Synthesis of isonitrile ligands The syntheses of the isonitriles suitable for providing isonitrile complexes of the general formula (II) can be accomplished by conventional methods, which are briefly outlined below, from precursors which are commercially available or can be obtained by known methods. Suitable methods for the formation of isonitriles are e.g. the elimination of water from N-substituted formamides, the reaction between primary amines and chloro-form under basic conditions (haloform-isocyanide transformation), and the reduction of isocyanates. A preferred method to provide isonitriles of the general formula R1-NEC is the reaction of an amine R1-NH2 with a formic acid ester at elevated temperature to obtain a formamide of the formula R1-NH-CH(=0) and the subsequent elimination of water, e.g. with POCI3 and a tertiary amine, phosgene and a tertiary amine, etc., as depicted in Scheme 1.
Scheme 1:
i NH 2 HCOOEt H P00I33 NEt3 C
R' R1N ,..- N ' R'l H
In Scheme 1 R1 has the aforementioned meanings, in particular the meanings men-tioned as preferred, Et means ethyl.
Synthesis of isonitrile complexes of the general formula (II) In the process of the invention the desired metal carbene complexes are prepared from metal coordinated isonitrile ligands (isocyanide ligands). The employed isonitrile com-plexes of the general formula (II) R1-NEC-M can be obtained e.g. from the aforemen-tioned isonitrile compounds R1-NEC and readily available complexes of a metal M by ligand exchange reactions known to a person skilled in the art as depicted in Scheme 2. Preferred educt complexes are e.g. [Pd(CH3CN)2Cl2], [Pt(CH3CN)2Cl2] and [AuCl(tetrahydrothiophene)].
Scheme 2 (Synthesis of the Pd(II)- and Au(I)- and Pt(II)-isonitrile complexes):

, ,,N
CI\ ,C
[Pd(CH3CN)2Cl2] + 2 CEN¨R1 ¨).- Pd / =
CI C , \\N
`RI

, CI\ ,C
[Pt(CH3CN)2Cl2] + 2 CEN¨R1 ¨3.- Pt / =
CI C \, \N
`RI
CI¨Au¨S + CEN¨R1 -3".' a -ALI -CN -R1 In Scheme 2, R1 has the aforementioned meanings, in particular the meanings men-tioned as preferred.
Synthesis of NHC complexes To obtain the desired NHC complexes, an isonitrile complex of the general formula (II) is reacted with a compound of the general formulae (111) or (111a) Z

y 5 _ n NH2 n N
Y _ R R6 X _ R5 R6 H
(III) (111a) wherein n, R2, R3, R4, R5, R6, R7 and R8 have one of the meanings given above, X- is an anion equivalent, and Y is a leaving group, or if R3 and R4 together with the carbon atom to which they are bound are 0=0 then Y is a group O-Ya, where Ya is unsubstituted or substituted alkyl, unsubstituted or substituted aryl, unsubstituted or substituted alkyl carbonyl, or unsubstituted or substituted arylcarbonyl.
1 0 The anion equivalent X- serves merely as counterion and can be selected freely from among monovalent anions and the parts of polyvalent anions corresponding to a single negative charge. Suitable anions are, for example, halide ions X-, e.g.
chloride and bromide, sulfate and sulfonate anions, e.g. S042-, tosylate, trifluoromethanesulfonate and methanesulfonate. Preferably, X- is chloride or bromide.
Preferably, Y is selected from halides, tosylates, carboxylates, carbonates, esters, sul-fonates and phosphates. Examples of Y are chlorine, bromine, iodine, methanesul-fonate, trifluoromethanesulfonate and toluenesulfonate, with preference given to chlo-rine and bromine.
Preferably, Ya is selected from 01-04 alkyl and pentafluorophenylcarbonyl.
In a first preferred embodiment, the compound of the formula (111) is an w-haloalkyl-ammonium salt, preferably a 2-(haloethyl)ammonium halide or a 3-(halopropyI)-ammonium halide. Likewise, in a further first preferred embodiment, the compound of the formula (III.a) is an w-haloalkylamine, preferably a 2-(haloethyl)amine or a 3-(halopropyl)amine.
In particular, the compound of the formula (111) is a 2-(chloroethyl)ammonium chloride of the formula (111.1) and the compound of the formula (III.a), is a 2-(chloroethyl)amine of the formula (111.1.a) + R3 R4 F-11 NHTR2 N, (111.1) (111.1.a) wherein R2 is selected from alkyl and cycloalkyl, in particular C1-C6-alkyl, phenyl-Ci-C6-alkyl and C5-Ci5-cycloalkyl.

R3, R4, R7 and R8 are selected from hydrogen, Ci-C6 alkyl and C6-Cio aryl.
Preferably, in the compounds (111.1) and (III.1.a), R2 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, cyclododecyl 10 and 1-adamantyl.
Preferably, in the compounds (111.1) and (111.1.a), R3, R4, R7 and R8 are selected from hydrogen and phenyl. In a special embodiment, R3, R4, R7 and R8 are all hydrogen. In a further special embodiment, 1 of the residues R3, R4, R7 and R8 is phenyl and the other 15 are hydrogen.
The syntheses of w-haloalkylammonium salts (111) and the free base thereof, i.e. CO-haloalkylamin compounds (III.a) can be accomplished by conventional methods, as depicted in Scheme 3 for the w-chloroalkylammonium salts. Thus, the synthesis of 2-20 (chloroethyl)ammonium chlorides can be accomplished according to literature proce-dures starting from commercially available amino alcohols (see e.g. A.
Habtemariam et al., J. Chem. Soc. Dalton Trans. 2001, 8, 1306 ¨ 1318). The free amine of the formula (III.1.a) is liberated from the salt of the formula (111.1) by addition of a base. Suitable bases are e.g. tertiary amines such as triethylamine.
Scheme 3 (Synthesis of 2-(chloroethyl)ammonium chlorides and 2-(chloroethyl)amin compounds) H¨R R4 2 SOC12 R>/F i\iH
i R2 base >/z\N R2 _______________________________ )...
HO Cl C I
(111.1) (III.1.a) In scheme 3, R2, R3, R4, R7 and R8 have the aforementioned meanings, in particular the meanings mentioned as preferred.
The synthesis of 2-(adamantan-1ylamino)ethanol as starting material for the formation of the corresponding 2-(chloroethyl)ammonium chloride can be performed as described by P. E. Aldrich, E. C. Herrmann, W. E. Meier, M. Pau!shock, W. W. Prichard, J. A.
Snyder and J. C. Watts in J. Med. Chem. 1971, 14, 535¨ 543.
In a second preferred embodiment, the compound of the formula (111) is an 0)-(alkoxycarbonyl)alkylammonium salt, preferably a 2-(Ci-C4-alkoxy-carbonyl)ethylammonium halide or a 3-(Ci-C4-alkoxycarbonyl)propylammonium halide.
Likewise, in a second preferred embodiment, the compound of the formula (III.a) is an w-(alkoxycarbonyl)alkylamine, preferably a 2-(Ci-C4-alkoxycarbonyl)ethylamine or a 3-(Ci-C4-alkoxycarbonyl)propylamine.
In particular, the compound of the formula (111) is a 2-(Ci-C4-alkoxy-carbonyl)ethylammonium chloride of the formula (111.2) and the compound of the formu-la (III.a) is a 2-(Ci-C4-alkoxycarbonyl)ethylamin of the formula (III.2.a) R3 R4 + R3 R4 F-11 (Ci-C4-alkyl)-0 (Ci-C4-alkyl)-0 R

(111.2) (III.2.a) wherein R2 is selected from alkyl and cycloalkyl, in particular Ci-C6-alkyl, phenyl-Ci-C6-alkyl and C5-Ci5-cycloalkyl.
R3, R4, R7 and R8 are selected from hydrogen, Ci-C6 alkyl and C6-Cio aryl.
Preferably, in the compounds (111.2) and (III.2.a), R2 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, cyclododecyl and 1-adamantyl.
Preferably, in the compounds (111.2) and (III.2.a), R3, R4, R7 and R8 are selected from hydrogen and phenyl. In a special embodiment, R3, R4, R7 and R8 are all hydrogen. In a further special embodiment, 1 of the residues R3, R4, R7 and R8 is phenyl and the oth-ers are hydrogen.
To obtain access to the desired NHC-complexes, the isonitrile complexes of the gen-eral formula (11) are reacted with a compound of the general formula (111) or (III.a).

Preferably, the reaction is performed in the presence of a base, more preferably a terti-ary amine, in particular triethylamine.
Suitable reaction temperatures are generally in the range from -10 to 100 C, preferably in the range from -0 to 50 C. In a preferred embodiment, the reaction is performed at ambient temperature.
The process in step al) of the invention can be carried out in a suitable solvent which is inert under the respective reaction conditions. Solvents which are generally suitable are, for example, aromatics such as toluene and xylenes, hydrocarbons or mixtures of hydrocarbons such as cyclohexane, ethers such as tert-butyl methyl ether, 1,4-dioxane and tetrahydrofuran, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ketones such as acetone and methyl ethyl ketone, etc.
Advantageously, the reaction of the invention shows full conversions to NHC
com-plexes (I). The reaction can be monitored e.g. by the shift of the IR-stretching frequen-cies of the isonitrile ligands. The method is also successful in the formation of bicyclic NHC complexes, e.g. by using piperidine or a derivative thereof as precursor.
Step bl) The compounds of the general formula (I), wherein R3 and R4 together with the carbon atom to which they are bound are C=0 and wherein the ring carbon atom adjacent to the carbonyl group bears a hydrogen atom are able to form the corresponding enol tautomers as depicted in scheme 4 for compounds (I-B.1) and (I-B.2). Those tautomers are also incorporated by the invention.
Scheme 4 (Keto-enol tautomers) 0 cKR H7 RiN N R2 R R2 (1-B.1) )-( (1-B.2) In Scheme 4, M, R1, R2, R6, R7 and R8 have the aforementioned meanings, in particular the meanings mentioned as preferred.
The enolizable compounds of the formula (I) obtained in step a) can be subjected to a further reaction with suitable electrophiles in step b1).
Accordingly, compounds of the general formula (I), wherein R3 and R4 together with the carbon atom to which they are bound are 0=0, can be subjected e.g. to a further reac-tion with a compound R3a-Z, where Z is a leaving group, in the presence of a suitable base. Preferably Z is selected from halides, tosylates, carboxylates, carbonates, esters, sulfonates and phosphates. Examples of Z are chlorine, bromine, iodine, methanesul-fonate, trifluoromethanesulfonate and toluenesulfonate, with preference given to chlo-rine and bromine.
The base employed in step b1) is preferably a non-nucleophilic base, more preferably a hindered alkali amide base, e.g. lithium diisopropylamide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide.
The reaction in step b1) is usually carried out at a temperature in the range from -78 C
to ambient temperature, preferably in the range from -78 to 0 C.
Step a2) In step a2) of the process according to the invention an isonitrile complex of the gen-eral formula (11) is reacted with an amine of the formula (V) ,rµ
r,10 I (V) N 0,R11 wherein R2, R3 and R8 have one of the meanings given above, especially one of the preferred ones; and R1 and R11 have one of the meanings given above; preferably R1 and R11 are methyl or ethyl or R1 and R11 together form an 1,2-ethylene or 1,3-propylene moiety, the carbon atoms of which may be unsubstituted or may all or in part be substituted by methyl groups.
to give an intermediate compound of the formula VI
R11\

R ------0 (VI) I-I, N, 2 N---/ R

M
where R1, R2, R3, R8, R10, R" and M have one of the meanings given above, especially one of the preferred ones.
The reaction is usually carried out in an inert organic solvent. Suitable solvents are halogenated hydrocarbons, such as dichloromethane or trichloromethane, and ethers, such as diisopropyl ether, tert.-butyl methyl ether, dioxane, anisole, tetrahydrofuran and dimethoxyethane. The reaction is usually carried out at temperatures of from 0 C to 80 C, preferably from 10 C to 40 C.
The reaction in step a2) can be monitored e.g. by the shift of the IR-streching frequen-cies of the isonitrile ligands. All of the yields were excellent.
According to a further special embodiment, the process depicted in step a2) is used for the formation of compounds of the formula VI, where R1 and R2 have different mean-ings.

Preferably, in the compounds of the formula VI, R1 is preferably selected from groups of the formulae IV.1 to IV.5, with particular preference given to the formulae IV.1 and IV.2. More preferably, R1 is selected from C1-C6-alkyl, phenyl and phenyl which carries 1, 2 or 3 radicals independently selected from Ci-C6-alkyl and chlorine. In particular 5 preferably, R1 is selected from tert.-butyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl and (2-chloro-6-methyl)phenyl.
Preferably, in the compounds of the formula VI, R2 is selected from alkyl and cycloalkyl, in particular Ci-C6-alkyl, phenyl-Ci-C6-alkyl and C5-Ci5-cycloalkyl. In particular, R2 is 10 selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, cyclopentyl, cyclohexyl, cyclododecyl and 1-adamantyl.
Preferably, in the compounds of the formula VI, R3 and R8 are independently of each other selected from hydrogen, Ci-C6-alkyl and C6-Cio-aryl.
Preferably, in the compounds of the formula VI, R1 and R11 are, independently of each other, selected from Ci-C4-alkyl.
Preferably, in the compounds of the formula VI, M is PdC12(CNR1), PtC12(CNR1), PdCI(CNR1)2, Au (CNR1) and AuCI, where R1 is selected from hydrogen, alkyl, cycloal-kyl, heterocycloalkyl, aryl and hetaryl. In particular, M is AuCl.
Compounds of the formula VI are novel and thus form also part of the invention. They usually are air and moisture stable and can be stored at room temperature without de-composition.
Step b2) In step b2), the intermediate compound of the formula (VI) is treated with an acid to obtain in situ the corresponding compound (VII) with a carbonyl functional group and subsequently intramolecular ring closure to obtain the compound of the formula 1-E as depicted in scheme 5.
Scheme 5:

¨ ¨

R \ R8 i) R8 IN ------0 R3 ii) ?-( __________________________ N.-H, N, 2 H, N, 2 RiNi\j----R2 N---/ R N--__./ R2 R1' M M
(I-E) (VI) (VII) In scheme 5, R1, R2, R3, R8, R10, R11 and M have one of the meanings given above, especially one of the preferred ones.
In step i) of scheme 5, compounds VI is treated with an acid to give the intermediate compound VII which reacts further to compound I-E in step ii). Suitable acids are inor-ganic or organic acids. Examples of suitable inorganic acids are mineral acids such as HCI or organic acids such as p-toluenesulfonic acid. Step i) of scheme 5 is usually car-ried out under hydrolytic conditions. Suitable solvents are those mentioned in step al).
The reaction temperature is usually in the range from -10 to 100 C, preferably in the range from 0 to 50 C.
Compounds of the formula V can be obtained as depicted in scheme 6.
Scheme 6:

r, ,rµii y o 3 R10 0 i) R3 0 ) R
iN R3H2 + 0I>\ R2N0IR11 R11/ (V) (VIII) (IX) In Scheme 6, R1, R2, R3, R8, R1 and R11 have one of the meanings given above, in par-ticular one of those being preferred.
In step i) of scheme 6, the amine R1-NH2 is treated with a compound of the formula (VIII) to give the imine of the formula (IX). The reaction is advantageously carried out in the presence of a dehydrating agent such as magnesium sulfate. The reaction is usu-ally carried out in the presence of a solvent. Suitable solvents are halogenated ali-phatic, alicyclic or aromatic hydrocarbons such as dichloromethane. In step ii) of scheme 6, the imine compound of the formula IX is reduced to yield the amine com-pound V. Suitable reducing agents are hydrides such as lithium aluminium hydride or sodium borohydride. The reaction is usually carried out in the presence of a solvent.
Suitable solvents are Ci-C4-alkanols, e.g. methanol or ethanol.
Step a3) In the process according to the invention, the desired NHC complexes according to variant a3) having the formula I-F, _____________________________ R

EWG )i R87 ( R
Ri NZrµ N----o2 (1-F) M
where R1, R2, R4, R7, R8, M and EWG have one of the meanings given above, prefera-bly one of the preferred ones, can be prepared by reacting the isonitrile complexes of the formula I la with an amine of the formula Illb or Illc H R7 R8 .144H44R8 Isisri-\( + ZR2 EWG

(111b) (111c) where R2, R4, R7 and R8 have one of the meanings given above;
X- is an anion equivalent; and EWG is C(0)R14, C(0)0R14, NO2, S(0)R14 or S(0)2R14, where R14 is hydrogen, alkyl, cycloalkyl or aryl.
The reaction is usually carried out in an organic solvent. Suitable organic solvents are aprotic solvents such as a haloalkanes, e.g dichloromethane.

The compounds of the general formula (I) according to the invention and/or obtained by the process of the invention can advantageously be employed in NHC metal complex catalyzed reactions. The compounds of the general formula (I) are preferably used as or in a catalyst employed in a C-C, C-0, C-N or C-H bond formation reaction.
They are especially used in a C-C coupling reaction, selected from the Suzuki reaction, Heck reaction, Sonogashira reaction, Stille reaction, Hartwig-Buchwald reaction and Kumada reaction. Further, they are especially used in a reaction, selected from the hydrogena-tion, hydroformylation, hydrosilylation, Hartwig-Buchwald reaction and amide a-arylation. (With regard to C-C bond formation by cross-coupling, see: S. P.
Nolan and O. Navarro in Comprehensive Organometallic Chemistry III, Vol. 11, 1st ed.
(Ed.: A.
Canty), Elsevier, Oxford, 2007, Chapter 11.01, 1-38, and references therein;
b) F.
Glorius, Top. Organomet. Chem. 2007, 21, 1-20; c) E. A. B. Kantchev, C. J.
O'Brien and M. J. Organ, Aldrichimica Acta 2006, 39, 97-111) Suzuki cross-coupling (Suzuki-Miyaura cross-coupling) The palladium-catalyzed cross-coupling reaction between organoboron compounds and organic halides or triflates provides a powerful and general method for the forma-tion of carbon-carbon bonds. For their fundamental work in the field of palladium-catalyzed cross couplings, the Nobel Prize in chemistry 2010 was awarded jointly to A.
Suzuki, R. F. Heck and E.i Negishi. Information on the use of NHC metal complexes in the Suzuki reaction can be found in: a) W.A. Herrmann, C.P. Reisinger, M.
Spiegler, J.
Organomet. Chem. 1998, 557, 93; b) C.M. Zhang, J.K. Huang, M.L. Trudell, S.P.
No-lan, J. Org. Chem. 1999, 64, 3804; c) A. Furstner, A. Leitner, Synlett. 2001, 290; d) C.W.K. Gstottmayr, V.P.W. Bohm, E. Herdtweck, M. Grosche, W.A. Herrmann, Angew.
Chem. Int. Ed. 2002, 41, 1363.
Preferably, the compounds of the general formula (I) are used in a reaction c (1) A C B
RB(RB)2 + R¨E ,..- R ¨R + E¨B(R)2 base wherein RA is selected from in each case unsubstituted or substituted alkyl, alkenyl, alkinyl and aryl, RB is selected from alkyl, alkoxy and hydroxyl, RC is selected from in each case unsubstituted or substituted alkyl, alkenyl and aryl, E is selected from CI, Br, I, CF3S03, (ORD)2P(=0)0, wherein RD is hydrogen, alkyl, cycloalkyl or aryl, the base is preferably selected from an alkali metal hydroxide, earth alkali metal hydroxide, alkali metal carbonate, earth alkali metal carbonate, thallium(I) hydroxide, thallium (I) alkanolate, alkali metal phosphate, alkali metal fluoride.
Examples for suitable bases are NaOH, KOH, Na2CO3, K2CO3, Cs2CO3, Ba(OH)2, K3PO4, TIOH, thallium(I) ethoxide, KF, CsF, (C4H9)4NF, sodium ethoxide, potassium ethoxide and potassium tert-butoxide.
In particular, the compounds of the general formula (I) are used in the following reac-tions B(OH)2 CH

0 (101 (01 (21 CH3 cat. 1101 KO(tert-C4H9) E = CI, Br B(OH)2 CH3 (101 H3 +C = CH, - cat.
KO(tert-C4H9) E = Cl, Br cat. catalyst of the formula (I) Sonogashira reaction The Sonogashira cross-coupling reaction is a palladium (and usually also copper) cata-lyzed coupling of terminal alkynes with aryl halides or vinyl halides to give enynes. In-formation on the use of NHC metal complexes in the Sonogashira reaction can be found in: a) S. Caddick, F.G.N. Cloke, G.K.B. Clentsmith, P.B. Hitchcock, D.
McKerre-cher, L.R. Titcomb, M.R.V. Williams, J. Organomet. Chem. 2001, 617; b) C.L.
Yang, S.P. Nolan, Organometallics 2002, 21, 1020; c) L. Ray, S. Barman, M.M. Shaikh, P.
Ghosh, Chem. Eur. J.2008, 14, 6646.

Preferably, the compounds of the general formula (I) are used in a reaction (I) RE ¨E + H¨CEC¨RFE -R ¨C=C¨RF
base 5 wherein RE is selected from in each case unsubstituted or substituted alkenyl, aryl and hetaryl, 10 RF is selected from hydrogen, alkyl, alkenyl, aryl and Si(RG)3, RG is selected from in each case unsubstituted or substituted alkyl, cycloalkyl and aryl, 15 E is selected from CI, Br, I, CF3S03, the base being usually an amine, alkanolate, earth alkali metal carbonate or alkalimetal carbonate. Preferably, the base is selected from secondary alkylamines, tertiary alkylamines, alkali metal alkanolates and alkali metal carbonates. The amine 20 compound may be used in excess and serves also as solvent.
Preferred solvents for the Sonogashira reaction are CH3CN, DMF
(dimethylformamide) THF (tetrahydrofuran) or ethyl acetate.
25 Preferred base for the Sonogashira reaction are N(C2H5)3, HN(C2H5)2, N(iso-C3F-17)2(C2H5), KO(tert-C4H9), K2CO3 and Cs2CO3.
In particular, the compounds of the general formula (I) are used for the reaction of bro-mobenzene and 1-hexyne. No additional copper source was used.
Information on the use of NHC metal complexes in the Heck reaction can be found in:
a) W.A. Herrmann, M. Elison, J. Fischer, C. Kocher, G.R.J. Artus, Angew. Chem.
Int.
Ed. 1995, 34, 2371; b) E.A.B. Kantchev, C.J. O' Brien, M.G. Organ, Angew.
Chem.
Int. Ed. 2007, 46, 2768; c) J. Ye, W. Chen, D. Wang, Dalton Trans. 2008, 30, 4015.
Information on the use of NHC metal complexes in the Stille reaction can be found in:
G.A. Grasa, S.P. Nolan, Org. Lett. 2001, 3, 119.

Information on the use of NHC metal complexes in the Kumada reaction can be found in: V.P.W. Bohm, T. Weskamp, C.W.K. Gstottmayr, W.A. Herrmann, Angew.
Chem. Int. Ed. 2000, 39, 1602.
Information on the use of NHC metal complexes in the Hartwig-Buchwald-reaction can be found in: a) S.R. Stauffer, S.W. Lee, J.P. Stambuli, S.I. Hauck, J.F.
Hartwig, Org.
Lett. 2000, 2, 1423, b) J. Huang, G. Grasa, S.P. Nolan, Org. Lett. 1999, 1, 1307.
Information on the use of NHC metal complexes in the a-arylation of amides can be found in: S. Lee, J.F. Hartwig, J. Org. Chem. 2001, 66, 3402.
Information on the use of NHC metal complexes in the hydrogenation can be found in:
a) H.M. Lee, T. Jiang, E.D. Stevens, S.P. Nolan, Organometallics 2001, 20, 1255; b) L.D. Vazquez-Serrano, B.T. Owens, J.M. Buriak, Chem. Comm. 2002, 2518; c) D.
Gnanamgari, E.L.O. Sauer, N.D. Schley, C. Butler, C.D. Incarvito, R.H.
Crabtree, Or-ganometallics 2009, 28, 321; d) H. Turkmen, T. Pape, F. Hahn, C. Ekkehardt;
Eur. J.
Inorg. Chem. 2008, 34, 5418.
Information on the use of NHC metal complexes in the hydroformylation can be found in: a) J.D. Scholten, J. Dupont, Organometallics 2008, 27, 4439.
Information on the use of NHC metal complexes in the hydrosilylation can be found in:
b) W.A. Herrmann, L.J. Goossen, M. Spiegler, J.Organomet. Chem. 1997, 547, 357.
The following examples illustrate the invention without restricting it.
Examples General methods All reagents and solvents were obtained from Acros, ABCR, Alfa Aesar, Sigma-Aldrich or VWR and were used without further purification unless otherwise noted.
Deuterated solvents were purchased from Euriso-Top. Absolute solvents were dried by a MB
SPS-800 with the aid of drying columns. Preparation of air- and moisture-sensitive materials was carried out in flame dried flasks under an atmosphere of nitrogen using Schlenk-techniques. Cross coupling reactions were performed in technical grade solvents. Thin layer chromatography (TLC) was performed using Polygram precoated plastic sheets SIL G/UV254 (5i02, 0.20 mm thickness) from Macherey-Nagel. Column chromatography was performed using silica gel (40.0-63.0 nm particle size) from Macherey-Nagel. NMR

spectra were recorded on Bruker Avance 500, Bruker Avance 300 and Bruker ARX-250 spectrometers. Chemical shifts (in ppm) were referenced to residual solvent pro-tons. Signal multiplicity was determined as s (singlet), d (doublet), t (triplet), q (quartet) or m (multiplet). 13C assignment was achieved via DEPT90 and DEPT135 or HSQC-me spectra. MS spectra were recorded on a Vakuum Generators ZAB-2F, Finnigan MAT
TSQ 700 or JEOL JMS-700 spectrometer. GC spectra were recorded on HP Agilent 5890 Series 11 Plus with FID analyser. GC-MS spectra were recorded on an Agilent 5890 Series 11 Plus with a HP 5972 mass analysator. IR spectra (in cm-1) were re-corded on a Bruker Vector 22 FT-IR. Crystal structure analysis was accomplished on Bruker Smart CCD or Bruker APEX diffractometers. Elemental analysis was performed on an Elementar Vario EL. ReactlR studies were performed on a ReactlR
Mettler Toledo IC10.
Syntheses 1. Preparation of starting materials 1.0 General synthesis of formamides R1 ¨NH2 ( 1 ) (2) R1 is as defined above.
The amine (1) was dissolved in ethyl formate (15 mL) and was heated in an autoclave at 200 C for 12h and at 250 C for another 5h. The precipitate was filtered off and washed with n-pentane. Recrystallisation from acetone/petrol ether (1/5) yielded the formamide compound (2) as colourless crystal.
1.1 Synthesis of isonitrile ligands 1.1.a General procedure for preparing isonitrile compounds Ri Nc (2) (3) R1 is as defined above.

The formamide (2) was dissolved in absolute dichloromethane. The solution was cooled to - 60 C and POCI3 was added dropwise over a period of 5 min. The suspen-sion was stirred for 20 min and triethylamine was added dropwise over 10 min.
The resulting yellow suspension was stirred overnight. During this time, the cooling bath was allowed to warm up to room temperature. Afterwards, the suspension was poured onto ice and warmed up to room temperature. Dichloromethane was added and the layers were separated. The organic layer was washed 3 times with a saturated aque-ous solution of NaHCO3. The organic phase was dried with Na2SO4 and the solvent was removed under reduced pressure. The crude product was purified by destillation or column chromatography (Si02).
Example I: 2,4,6-trimethylphenyl isonitrile 2,4,6-trimethylaniline (10 g, 73.9 mmol) was dissolved in ethylformiate (15 ml). The mixture was heated in an autoclave at 200 C for 12 h. After this, the solid precipitate was filtered off and washed with pentane. Recrystallization from acetone/petrolether (1/3) yielded N-(2,4,6-trimethylphenyl)formamide as colourless crystals in almost quan-titative yield (11.43 g, 96%). All analytical data are in good agreement with the previ-ously reported ones (G. Vougioukalakis, J. Am. Chem. Soc. 2008, 130, 2234-2245).
The formamide (1g, 6.13 mmol) was dissolved in absolute dichloromethane (DCM) (30 ml). The solution was cooled to -60 C in an ethanol/liquid nitrogen bath and POCI3 (1.67 ml, 18.3 mmol) was added drop wise over a period of 5 min. The suspension was stirred for 20 min and triethylamine (5.57 g, 55.0 mmol) was added drop wise over 10 min. The resulting yellow suspension was stirred over night. During this time, the cool-ing bath was allowed to warm up to room temperature. Afterwards, the suspension was poured onto ice and warmed up to room temperature. DCM (30 ml) was added and the layers were separated. The organic layer was washed with a saturated solution of Na-HCO3 (3x10 ml). The organic phase was dried with NaSat and the solvent was re-moved under reduced pressure. The crude product was purified by sublimation (50-55 C, 6.5x10-2 mbar) to yield the title compound as colourless crystals (637 mg, 72%).
1H NMR (300 MHz, CD2Cl2): 6 = 2.23 (s, 3 H, -CH3), 2.31 (s, 6 H, -CH3), 6.95 (s, 2 H, ArH); 13C NMR (75 MHz, CD2Cl2): 6 = 17.19, 19.53, 127.01, 133.16, 137.55 (no further signals observed). All analytical data are in good agreement with previously reported ones (G. Vougioukalakis, J. Am. Chem. Soc. 2008, 130, 2234-2245).
Example II: 2,6-diisopropylphenyl isonitrile 2,6-diisopropylaniline (purity: 92%,10 g, 51.9 mmol) was dissolved in ethylformiate (15 ml). The mixture was heated in an autoclave first at 200 C for 12 h after this at 250 C

for 5 h. The solid precipitate was filtered off and washed with pentane.
Recrystallization from acetone/petrol ether (1/5) yielded N-(2,6-diisopropylphenyl)formamide as colour-less crystals in almost quantitative yield (9.48 g, 46.2 mmol, 89%). The formamide (1 g, 4.87 mmol) was dissolved in absolute DCM (10 m1). The solution was cooled to -in an ethanol/liquid nitrogen bath and POCI3 (1.33 ml, 14.6 mmol) was added drop wise over a period of 5 min. The suspension was stirred for 20 min and triethylamine (4.43 g, 43.8 mmol) was added drop wise over 10 min. The resulting yellow suspension was stirred over night. During this time, the cooling bath was allowed to warm up to room temperature. Afterwards, the suspension was poured onto ice and warmed up to room temperature. DCM (30 ml) was added and the layers were separated. The organic layer was washed with a saturated solution of NaHCO3 (3x10 m1). The organic phase was dried with Na2SO4 and the solvent was removed under reduced pressure. The crude product was purified by distillation (72-80 C, 4.5x10-2 mbar) to yield the title compound as colourless oil (720 mg, 3.84 mmol, 79%).
1H NMR (300 MHz, CD2Cl2): 6 = 1.22 (d, 12 H, J= 7.0 Hz, -CH3), 3.32 (m, 2 H, J= 6.9 Hz, -CH-), 7.14 (d, 2 H, J= 7.8 Hz, ArH), 7.29 (t, 1 H, J= 7.7 Hz, ArH); 13C
NMR (75 MHz, CD2Cl2): 6 = 23.12, 30.62, 123.94, 130.05, 145.72 (no further signals observed).
All analytical data are in good agreement with previously reported ones (U. J.
Kilgore, F. Basuli, J. C. Huffman, D. J. Mindiola, Inorg. Chem. 2006, 45, 487-489).
1.2 Synthesis of isonitrile-Pd complexes General procedure:
[Pd(CH3CN)2Cl2] was dissolved in toluene and two equivalents of the isonitrile was added. The mixture was stirred 12 h at room temperature. The precipitate was filtered off, washed with cold pentane and dried under reduced pressure to afford the title compounds.
Example III: cis-[PdC12(2,6-dimethylphenyl isonitrile)2]
[Pd(CH3CN)2Cl2] (200 mg, 780 pmol) was dissolved in toluene (8 ml) and 2,6-dimethylphenyl isonitrile from example 11 (212 mg, 1.60 mmol) was added. The mixture was stirred 12 h at ambient temperature. The precipitate was filtered off, washed with cold pentane (3x10 ml) and dried under reduced pressure to yield the title compound as white solid (333 mg, 757 pmol, 97%).
IR (KBr): v = 2363, 2208, 1632, 1473, 1384, 1170, 771, 717, 576, 499,453; HRMS
(FAB+) C181-118N2C1Pd [M-C1]+: calc. 403.0193, found: 403.0138.
The compounds of the examples IV, V, VI and VII listed below were prepared in an analogous manner to example 111.

Example IV: cis-[Pd(2,4,6-trimethylphenyl isonitrile)2C12]
The title compound was obtained as white solid (yield: 89%).
IR (KBr): v = 2919, 2210, 1604, 1471, 1382, 1308, 1035, 853, 712, 600, 568, 502, 5 473; HR-MS (FAB+): calc.: C201-122PdCIN3 [M-CI]+= 431.0506, found:
431.0486 Example V: cis-[PdC12(2,6-diisopropylphenyl isonitrile)2]
The title compound was obtained as a yellow solid (yield: 83%).
1H NMR (300 MHz, CD2Cl2): 6 = 1.21 (d, 12 H, J= 6.9 Hz, -CH3), 3.26 (m, 2 H, -CH-), 10 7.17 (d, 2 H, J= 7.8 Hz, ArH), 7.40 (t, 1 H, J= 7.9 Hz, ArH); 13C NMR
(75 MHz, CD2Cl2):
6 = 23.24 (q, 8C), 30.78 (d, 4C), 124.77 (d, 6C), 132.52 (s, 4C), 147.24 (s, 2C);
IR (KBr): v = 2966. 2927. 2873, 2209, 1635, 1585, 1475, 1458, 1433, 1388, 1366, 1356, 1259, 1183, 1062, 800, 751, 510, 477 cm-1; HR-MS (FAB+): m/z = 515.1140, calcd. for C26H34CIN2Pd [M- Cl- ]+: 515.1145, m/z =480.1760, calcd. for C26H34N2Pd 15 [M- 2C1- ]+: 480.1757.
Example VI: cis-[PdC12(2-chloro-6-methylphenyl isonitrile)2]
The title compound was obtained as a white solid (yield: 95%).
1H NMR (300 MHz, CDCI3): 6 = 2.45 (s; 3 H, -CH3), 7.09 - 7.26 (m; 3 H, ArH);
IR
20 (KBr): v = 2206, 1632, 1461, 1177, 873, 782, 711, 56913C NMR (75 MHz, CDCI3): 6 =
19.34, 77.43, 127.96, 129.19, 129.59, 131.78, 132.09, 139.68; HRMS (FAB+) C161-112N2C13Pd [M-C1]+: calc. 442.9101, found: 442.9069 Example VII: cis-[PdC12(tert-buty1)2]
25 The title compound was obtained as a white solid (yield 92%). The analytical data are in good agreement with the previously reported ones S. Otsuka, Y. Tatsuno, K.
Ataka, J. Am. Chem. Soc 1971, 93, 6705-6706.
1.3 Synthesis of isonitrile-Au(I) complexes General procedure:
One equivalent of [AuCl(tetrahydrothiophene)] was dissolved in dichloromethane (DCM) and 1 equiv. isonitrile was added at room temperature. The mixture was stirred for 15 min. The solvent was removed under reduced pressure. The crystalline crude product was used without further purification.
Example VIII: [AuC1(2,4,6-trimethylphenyl isonitrile)]
[AuCl(tetrahydrothiophene)] (500 mg, 1.56 mmol) was dissolved in DCM (10 ml) and 2,4,6-trimethylphenyl isonitrile from example! (233 mg, 1.56 mmol) was added.
The mixture was stirred 12 h at ambient temperature. After this, the solvent was removed and the resulting white precipitate was washed with pentane (3x10 ml) to yield the complex as white solid (583 mg, 1.54 mmol, 99%).
1H NMR (300 MHz, CD2Cl2): 6 = 2.28 (s, 6 H, CH3), 2.34 (s, 3 H, CH3), 6.95 (s, 2 H, ArH); 13C NMR (75 MHz, CD2Cl2): 6 = 18.76, 21.59, 129.50, 136.42, 142.30; IR
(KBr):
v = 2917, 2207 (-NC), 1602, 1474, 1387, 1308, 1201, 1040, 857, 753, 713, 567, 493;
HR-MS (FAB+): calc.: C10H12AuCIN [M+H]= 378.0324, found: 378.0332.
The compounds of the examples IX and X listed below were prepared in an analogous Example IX: [AuC1(2,6-diisopropylphenyl isonitrile)]
The title compound was obtained in a yield of 99%.
1H NMR (300 MHz, CD2Cl2): 6 = 1.24 (d, 12 H, J= 6.9 Hz, -CH3), 3.2 (m, 2 H, J=
6.8 Hz, found: 384.1030 Example X: [AuCl(tert-butyl isonitrile)]
The title compound was obtained in a yield of 99%. All analytical data are in good agreement with the previously reported ones R. Heathcote, J. A. S. Howell, N.
Jennings, D. Cartlidge, L. Cobden, C. Coles, M. Hursthouse, Dalton Trans.
2007, 13, 1309-1315.
1.4 Synthesis of isonitrile-Pt(II) complexes General procedure:
Example XI: cis-[PtC12(2,6-diisopropylphenyl isonitrile)2]

7.22 (d, 2 H, J= 7.8 Hz, ArH), 7.42 (t, 1 H, J= 7.8 Hz, ArH), 13C-NMR (125 MHz, CD2C12): 6 = 22.89 (q, 8C), 30.38 (d, 4C), 124.31 (d, 6C), 131.72 (s, 4C), 146.67 (s, 2C); IR (KBr): v = 2966, 2929, 2869, 2219, 2189, 1475, 1465, 1457, 1436, 1386, 1365, 1184, 1062, 938, 804, 797, 747, 736, 491 cm-1; HR-MS (FAB+): m/z =
604.2060, calcd. for C26H34CIN2Pt [M- Cl- ]: 604.2058, m/z = 569.2372, calcd. for C26H34N2Pt [M- 2C1- ]: 569.2370..
1.5 2-(Chloroethyl)ammonium chlorides of the general formula III (Y = Cl) \ +
H¨R2 ____________________________ a- h¨R2 HO DCM CI H
R7 R R7 Ra CI
R2, R3, R4, R7 and R8 have the aforementioned meanings, DCM is dichloromethane.
The synthesis of the 2-(chloroethyl)ammonium chlorides has been accomplished ac-cording to literature procedures, e.g. A. Habtemariam, B. Watchman, B. S.
Potter, R.
Palmer, S. Parsons, A. Parkin, P. J. Sadler, J. Chem. Soc., Dalton Trans.
2001, 8, 1306-1318 starting from commercially available amino alcohols.
1.6 Synthesis of amino alcohols Example XII: 2-(adamantan-1ylamino)ethanol 1-Adamantylamine (1 g, 6.05 mmol) and 2-iodoethanol (1.20 g, 7.00 mmol) were dis-solved in benzonitrile (2 m1). The mixture was heated at 120 C for 12 h.
After this, the precipitate was filtered off and carefully washed with petrolether (3x20 m1).
The white solid was dissolved in DCM (30 ml) and washed with a saturated solution of Na2CO3 (3x 50 m1). The organic layer was separated, dried with Na2504 and the solvent was removed under reduced pressure to yield the title compound as colourless oil (950 mg, 4.86 mmol, 80 %).
1H NMR (250 MHz, CD2C12): 6 = 1.55 (m, 12 H, -CH2-), 1.99 (bs, 5 H, -CH- and over-lapping OH, NH), 2.65 (t, 2 H, J= 5 Hz, -CH2-), 3.44 (t, 2 H, J= 5.1 Hz, -CH2-); all spec-troscopic data are in good agreement with previously reported ones, e.g. P. E.
Aldrich, E. C. Herrmann, W. E. Meier, M. Paulshock, W. W. Prichard, J. A. Snyder, J. C.
Watts, J. Med. Chem. 1971, 14, 535-543.
1.7 Preparation of N-(2,2-dimethoxyethyl)amines of the general formula V

R-10\
0 R-10\

Ral 0 " \
R2NH2 1 ' R2 NCR

RNic,,R-11 R (6) R
R11/ (4) (5) R2, R3, R8, R1 and R11 have the aforementioned meanings.
In a typical protocol, one equivalent of the amine R2NH2 was dissolved in dichloro-methane and MgSat and 1.5 equivalents of compoun (4) were added. The mixture was stirred for 12 h at room temperature. Afterwards, the MgSat was filtered off and the solvent evaporated. The analytically pure imines were used without further purification.
The obtained imines were dissolved in dry methanol and 2 equiv. of NaBF14 were added at 0 C. After removal of the ice bath, the mixture was stirred for another 2 h. The reac-tion was quenched with water, diluted with dichloromethane and the organic phase was washed with saturated NH4CI solution and brine. The crude product was purified by distillation or column chromatography (Si02) to give the title compound Example XIII: N-(2,2-Dimethoxyethyl)-2,4,6-trimethylaniline The title compound was prepared according to the general procedure using 2.50 g (18.5 mmol) of mesitylamine, 3.2 g (27.3 mmol) of 2,2-dimethoxyacetaldehyde (60 % in water) and 3.00 g of MgSat in 100 ml of dichloromethane. After filtration of the solvent, N-(2,2-dimethoxyethylidene)-2,4,6-trimethylaniline was afforded as a yellowish solid;
yield: 4.05 g (18.3 mmol, 99%). 1H-NMR (300 MHz, CDCI3): 6 = 2.07 (s, 6H, CH3), 2.24 (s, 3H, CH3), 3.31 (s, 6H, OCH3), 4.87 (d, J = 4.5 Hz, 1H, CH(OMe)2), 6.83 (s, 2H, ArH), 7.42 (d, J= 4.5 Hz, 1H, CH=N); 13C-NMR (75 MHz, CDCI3): 6 = 18.31 (q, 2C), 20.79 (q), 54.32 (q, 2C), 103.61 (d), 125.82 (d, 2C), 128.87 (s, 2C), 133.52 (s), 147.53 (s), 163.5 (d); IR (KBr): v = 3431, 2999, 2955, 2914, 2836, 1667, 1480, 1455, 1442, 1375, 1308, 1215, 1194, 1147, 1098, 1065, 1004, 983, 849, 782 cm-1; HR-MS
(El):
m/z = 221.1388, calcd. for Ci3H1902N [M]: 221.1416.
N-(2,2-dimethoxyethylidene)-2,4,6-trimethylaniline (2.40 g, 10.9 mmol) was dissolved in 50 ml of dry methanol under an atmosphere of nitrogen and 533 mg of NaBF14 (14.1 mmol) was added. After workup the crude product was purified by destillation (120 C, 6x10-2 mbar); yield: 2.12 g (mmol, 87.1%); 1H-NMR (300 MHz, CDCI3): 6 = 2.27 (s, 3H, CH3), 2.31 (s, 6H, CH3), 3.12 (d, J= 6.4 Hz, 1H, CH(OMe)2), 3.26 (bs, NH), 3.44 (s, 6H, OCH3), 4.51 (t, J = 6.4 Hz, 2H, CH2), 6.86 (s, 2H, ArH); 13C-NMR (75 MHz, CDCI3):
6 = 18.27 (q, 2 C), 20.57 (q), 49.73 (t), 53.74 (q, 2C), 103.46 (t), 129.43 (d, 2C), 131.38 (q, 2C), 131.38 (d), 143.05 (s); IR (KBr): v = 3379,2936, 2856, 2832, 1486, 1447, 1376, 1306, 1236, 1194, 1157, 1131, 1074, 1034, 977, 924, 854, 739, 564 cm- 1;
HR-MS (El): nilz = 223.1573, calcd. for C13H2102N [M]: 223.1572.
1.8 Synthesis of compounds of formuala Illb with EWG being CO(0)CH3 Example XIV: (E)-Methyl 4-(cyclododecylamino)but-2-enoate NH
0)..' Under an atmosphere of nitrogen (E)-methyl 4-bromobut-2-enoate (5.70 g, 31.8 mmol), cyclododecanamine (6.41 g, 35.0 mmol) and Cs2CO3 were suspended in absolute tet-rahydrofuran (THF) (150.0 m1). The mixture was heated at reflux for 12 h and (saturated solution, 100 ml) was added. The mixture was extracted with DCM
(three times, 50.0 m1). The organic layer was dried with Na2SO4 and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using silica and petrol ether/ethyl acetate (4:1) to yield the title compound as yellow solid (5.54 g, 19.7 mmol, 62 %). 1H NMR (300 MHz, CD2Cl2) 6= 1.07-1.54 (m, 23 H, -CH2-, -NH-), 2.67 (m, 1 H, -CH-), 3.44 (dd, J=5.4, 2.2 Hz, 2 H, -CH2-), 3.75 (s, 3 H, -CH3), 6.02 (dd, J= 15.7, 2.1 Hz, 1 H, =CH-), 7.01 (dq, J= 15.7, 5.2 Hz, 1 H, =CH-).
11. Synthesis of NHC-(transition metal) complexes of the formula!
11.1 Synthesis of NHC-(transition metal) complexes of the formula 1-A.2.1 11.1.1 Synthesis of NHC-Pd(II) complexes General procedure for the synthesis of NHC-Pd(II) complexes In a typical protocol the cis-(isonitrile)-Pd(11) complex (321 pmol) and the 2-(chloroethyl)ammonium chloride (350 pmol) were suspended in absolute THF.
triethyl amine (0.5 ml, 6.81 mmol) was added. The mixture was stirred for 12 h at ambient temperature. After this all the volatiles were removed under reduced pressure and the solid was dissolved in DCM (20 m1). The solution was extracted with a saturated solu-tion of NH4CI (20 m1). The organic layer was dried with Na2504 and the solvent was removed under reduced pressure. The crude product was dissolved in a minimum of DCM and covered with a layer diethyl ether, inducing crystallization of the NHC-Pd(II) complexes as colourless crystals. The crystals were filtered off, washed with diethyl ether and dried under reduced pressure. All the complexes of examples 1 to 15 listed below in table I are air and moisture stable compounds and can be stored at ambient temperature without decomposition.
Table I

RiIA
N N----012 (1-A.2.1) with M being PdC12(CNR1) .0 -:-----C-"Pd CI

Ex. R1 R3 R2 R7 yield / material prop-erty 1 2,6-dimethylphenyl H methyl H 85%, colourless crys-tals 2 2,6-dimethylphenyl H isopropyl H 89%, colourless solid, 3 2,6-dimethylphenyl H cyclohexyl H 78%, colourless solid 4 2,6-dimethylphenyl phenyl cyclohexyl H 49%, yellow solid 5 2,4,6-trimethylphenyl H isopropyl H 96%, colourless solid 6 2,6-diisopropylphenyl H isopropyl H 83%, colourless solid 7 2,6-diisopropylphenyl H cyclohexyl H 95%, colourless solid 8 2,6-diisopropylphenyl H 1-adamantyl H 95%, colourless solid 9 2,6-diisopropylphenyl phenyl cyclohexyl H 60%, colourless solid 10 tert-butyl H methyl H 72%, colourless solid 11 tert-butyl H isopropyl H 69%, colourless solid 12 tert-butyl H cyclohexyl H 52%, colourless solid 13 2-methyl-6-chlorophenyl H methyl H 58%, dark crystals 14 2,6-dimethyl phenyl H -CH=CH-CH=CH- 58%, colourless solid 15 2,6-diisopropylphenyl H cyclopenta- H 42%, colourless solid decyl The physicochemical data of the complexes of the examples 1 to 14 are listed below:
10 Example 1:
1H NMR (300 MHz, DMS0): 6 = 2.06 (s; 3 H, -CH3), 2.30 (s; 6 H, -CH3), 2.44 (s;
3 H, -CH3), 3.52 (s; 3 H, -CH3), 3.98 (m; 4 H, -CH2-), 7.25 (m; 6 H, ArH); 130 NMR
(75 MHz, DMS0): 6 = 17.35, 17.93, 18.68, 37.20, 51.05, 51.20, 128.31, 128.42, 128.93, 129.06, 130.68, 135.33, 135.62, 136.77, 137.71, 182.03; IR (KBr): v = 3443, 2951, 2919, 2195, 1631, 1541, 1491, 1473, 1411, 1383, 1317, 1276, 1116, 780, 734, 619;
HRMS
(FAB+) C19H25N3CIPd [M-C1]+: calc. 460.0772, found: 460.0763.
Example 2:
1H NMR (600 MHz, CD2Cl2): 6 = 1.34 (d, 3 H, J= 6.8 Hz, -CH3), 1.39 (d, 3 H, J=
6.7 Hz, -CH3), 2.01 (s, 3 H, -CH3), 2.27 (s, 6 H, -CH3), 2.47 (s, 3 H, -CH3), 3.82-3.91 (m, 4 H, -CH2-), 5.40 (m, 1 H, J= 6.9, 6.3 Hz, -CH-), 6.94 (dd, 1 H, J= 7.3, 1.9 Hz, ArH), 7.1 (d, 2 H, J= 7.6 Hz, ArH), 7.17-7.27 (m, 3 H, ArH); 13C NMR (125 MHz, CD2Cl2): 6 =
18.11, 18.92, 19.40, 20.13, 20.93, 43.61, 51.02, 52.25, 128.65, 128.70, 129.62, 130.01, 130.70, 135.64, 136.19, 137.30, 138.70,184.22; 15N NMR (600 MHz, CD2Cl2, urea): 6 =
131.78, 148.43, 171.32; IR (KBr): v = 2970, 2925, 2358, 2195 (-NC), 1633, 1509, 1467, 1368, 1314, 1271, 1192, 1127, 1102, 1056, 935, 782, 623, 602, 569; HR-MS
(FAB+):
calc.: C23H29CIN3Pd [M-CI]+= 488.1085, found: 488.1104.
Example 3:
1H NMR (300 MHz, CD2Cl2): 6 = 0.98-1.86 (m, 10 H, -CH2-), 1.98 (s, 3 H, -CH3), 2.23 (s, 6 H, -CH3), 2.44 (s, 3 H, -CH3), 3.81 (m, 4 H, -CH2-), 4.87 (tt, 1 H, J=
10.7, 3.8 Hz, -CH-) 6.9 (dd, 1 H, J= 6.6 Hz, ArH), 7.07 (d, 2 H, J= 8.4 Hz, ArH), 7.12 (m, 3 H, ArH);
13C NMR (75 MHz, CD2Cl2): 6 = 18.49, 19.23, 19.80, 25.91, 26.04, 26.12, 31.18, 32.07, 45.24, 51.33, 60.10, 129.02, 129.06, 129.99, 130.38, 131.05, 136.04, 136.57, 139.11, 184.56; IR (KBr): v = 2931, 2855, 2193 (-NC), 1632, 1510, 1454, 1380, 1333, 1300, 1272, 1170, 1100, 1032, 990, 894, 780, 623, 570; HR-MS (FAB+): calc.:
C26H33CIN3Pd [M-CI]+= 530.1398, found: 530.1397.
Example 4:
(Mixture of diastereoisomers) 1H NMR (300 MHz, CD2Cl2): 6 = 1.05-1.81 (m, 10 H, -CH2), 1.92 (s, -CH3), 2.06 (s, -CH3), 2.17 (s, -CH3), 2.39 (s, -CH3), 2.55 (s, CH3), 4.03 (dd, J= 11.3, 5.6 Hz, -CH2), 4.15 (dd, J= 11.3, 6.0 Hz, -CH2), 4.33 (t, J=
11.3 Hz, -CH2), 4.88 (dd, J= 11.8, 5.6 Hz, -CH-), 5.03 (dd, J= 11.6, 6.0 Hz, -CH-), 5.16 (m, 1 H, -CH-), 6.73 (m, 1 H, ArH), 6.96-7.32 (m, 10 H, ArH); 13C NMR (75 MHz, CD2Cl2): 6 =
18.27, 18.51, 18.81, 19.08, 19.71, 19.87, 25.10, 25.44, 25.48, 30.24, 30.75, 31.38, 31.77, 50.75, 52.29, 59.58, 59.99, 66.51, 66.56, 77.44, 127.98, 128.01, 128.30, 128.49, 129.07, 129.20, 129.27, 129.57, 129.68, 129.90, 130.36, 130.45, 183.36, 183.98; IR
(KBr): v = 3031, 2932, 2855, 2193, 1631, 1509, 1474, 1453, 1416, 1382, 1296, 1250, 1210, 1168, 1101, 1034, 998, 780, 701; HR-MS (FAB+): calc.: C32H37CIN3Pd [M-CI]+=
604.1711, found: 604.1722 Example 5:

1H NMR (300 MHz, CD2Cl2): 6 = 1.32 (d, 3 H, J= 6.9 Hz, -CH3), 1.37 (d, 3 H, J=
6.6 Hz, -CH3), 1.95 (s, 3 H, -CH3), 2.22 (s, 6 H, -CH3), 2.25 (s, 3 H, -CH3), 2.26 (s, 3 H, -CH3), 2.41 (s, 3 H, -CH3), 3.71-3.92 (m, 4 H, -CH2-), 5.38 (m, 1 H, J= 6.8 Hz, -CH-), 6.73 (s, 1 H, ArH), 6.90 (s, 2 H, ArH), 7.00 (s, 1 H, ArH); 13C NMR (75 MHz, CD2Cl2): 6 =
18.37, 19.14, 19.67, 20.50, 21.27, 21.58, 21.88, 43.86, 51.42, 52.53, 58.95, 129.69, 129.75, 131.02, 135.09, 135.56, 136.25, 138.54, 139.96, 141.77, 184.74; IR (KBr): v =
2971, 2193, 1608, 1510, 1458, 1382, 1314, 1271, 1197, 1105, 1058, 855, 713, 625, 599, 573, 460, 428; HR-MS (FAB+): calc.: C25H33CIN3Pd [M-CI]+= 516.1398, found: 516.1391 Example 6:
1H NMR (300 MHz, CD2Cl2): 6 = 1.05 (d, 3 H, J= 3.3 Hz, -CH3), 1.07 (d, 3 H, J=
3.4 Hz, -CH3), 1.13 (d, 3 H, J= 7.0 Hz, -CH3), 1.19 (d, 6 H, J= 6.8 Hz, -CH3), 1.21 (d, 6 H, J=
6.8 Hz, -CH3), 2.88 (m, 1 H, J= 6.8 Hz, -CH-), 3.24 (m, 3 H, -CH-), 3.71-4.01 (m, 4 H, -CH2-), 5.47 (dm, 1 H, J= 7.0, 6.6 Hz, -CH-), 7.18, 7.17 (dd, 1 H, J= 7.7, 1.4 Hz, ArH), 7.19 (d, 2 H, J= 7.7 Hz, ArH), 7.29 (dd, 1 H, J= 7.8, 1.7 Hz, ArH), 7.40 (m, 2 H, ArH);
13C NMR (75 MHz, CD2Cl2): 6 = 20.65, 21.17, 23.49, 23.63, 23.87, 24.51, 27.22, 27.26, 29.29, 29.54, 30.36, 43.67,53.03, 124.73, 125.01, 126.19, 130.76, 131.80, 134.57, 146.85, 146.96, 149.31, 185.97; IR (KBr): V = 2965, 2930, 2870, 2185, 1497, 1459, 1433, 1386, 1366, 1348, 1331, 1315, 1267, 1184, 1113, 1058, 806, 751, 628; HR-MS
(FAB+): calc.: C311-145CIN3Pd [M-CI]+= 600.2337, found: 600.2335 Example 7:
1H NMR (500 MHz, CD2Cl2): 6 = 1.03 (d, 3 H, J= 6.9 Hz, -CH3), 1.04 (d, 3 H, J=
6.9 Hz, -CH3), 1.11 (d, 3 H, J= 6.9 Hz, -CH3), 1.17 (d, 6 H, J= 6.8 Hz, -CH3), 1.20 (d, 6 H, J=
6.8 Hz, -CH3), 1.34 (d, 3 H, J= 6.7 Hz, -CH3), 1.42-1.73 (m, 6 H, -CH2-), 1.85 (m, 3 H, -CH2-), 2.86 (m, 1 H, J= 6.8 Hz, -CH-), 3.21 (m, 2 H, J= 6.9 Hz, -CH-), 3.27 (m, 1 H, -CH-), 4.93 (tt, 1 H, J= 11.4, 3.7 Hz, -CH-), 7.15 (dd, 1 H, J= 7.7, 1.3 Hz, ArH), 7.18 (d, 2 H, J= 7.9 Hz, ArH), 7.28 (dd, 1 H, J= 7.8, 1.4 Hz, ArH), 7.39 (td, 2 H, J=
7.8, 2.1 Hz, ArH); 13C NMR (75 MHz, CD2Cl2): 6 = 20.65, 21.17, 23.49, 23.63, 23.87, 24.51, 27.22, 27.26, 29.29, 29.54, 30.36, 43.69, 53.03, 124.73, 125.01, 126.19, 130.76, 131.80, 134.57, 146.85, 146.96, 149.31, 185.97; IR (KBr): V = 2963, 2931, 2867, 2188, 1589, 1500, 1458, 1386, 1365, 1336, 1304, 1269, 1184, 1111, 1055, 804, 750, 731, 626; HR-MS (FAB+): calc.: C34H49CIN3Pd [M-CI]+= 640.2650, found: 640.2672 Example 8:
1H NMR (300 MHz, CDCI3): 6 = 1.0 (d, 3 H, J= 6.8 Hz, -CH3), 1.02 (d, 3 H, J=
6.9 Hz, -CH3), 1.07 (d, 3 H, J= 6.9 Hz, -CH3), 1.17 (d, 6 H, J= 6.9 Hz, -CH3), 1.19 (d, 6 H, J=
6.9 Hz, -CH3), 1.4 (d, 3 H, J= 6.4 Hz, -CH3), 1.69 (m, 6 H, -CH2-), 2.23 (m, 3 H, -CH-), 2.43 (m, 3 H, -CH-, -CH2-), 2.74 (m, 3 H, -CH-, -CH2-), 2.86 (m, 1 H, J= 6.8 Hz, -CH-), 3.24 (m, 2 H, J= 6.8 Hz, -CH-), 3.36 (m, 1 H, -CH-), 3.66-4.01 (m, 4 H, -CH2-), 7.06 (dd, 1 H, J= 7.7, 1.6 Hz, ArH), 7.12 (d, 2 H, J= 7.8 Hz, ArH), 7.25 (dd, 1 H, J=
7.8, 1.8 Hz, ArH), 7.33 (td, 2 H, J= 7.9, 2.8 Hz, ArH);13C NMR (75 MHz, CDCI3): 6 = 23.09, 23.33, 23.57, 24.14, 27.01, 27.10, 28.94, 29.16, 29.75, 30.02, 36.12, 42.96, 45.90, 52.74, 59.42, 124.04, 124.06, 125.93, 130.17, 131.02, 135.49, 145.74, 146.33, 148.95, 184.88; IR (KBr): v =2965, 2911, 2869, 2186, 1630, 1478, 1456, 1386, 1363, 1330, 1305, 1256, 1190, 1100, 1056, 804, 751, 620; HR-MS (FAB+): calc.: C38H53CIN3Pd [M-CI]+= 692.2963, found: 692.2974 Example 9:
(Mixture of diastereoisomers); 1H NMR (300 MHz, CD2Cl2): 6 = -0.14 (d, J= 6.6 Hz, -CH3), -0.06 (d, J= 6.8 Hz, -CH3), 0.79 (d, J= 6.8 Hz, -CH3), 1.06-1.99 (m, 29 H), 1.56-3.11 (m, 3 H, -CH2-), 3.44 (m, J= 6.6 Hz, -CH-), 3.87 (dd, J= 11.4, 4.0 Hz, -CH2-), 4.01 (m, -CH2-), 4.36 (m, -CH2-), 4.88 (dd, J= 11.2, 4.0 Hz, -CH-), 5.11 (m, -CH-), 6.97-7.45 (m, 11 H, ArH); 13C NMR (75 MHz, CD2Cl2): 6 = 22.46, 22.80, 23.54, 23.62, 23.85, 24.51, 24.73, 25.00, 25.50, 25.58, 25.77, 26.49, 26.79, 26.90, 28.87, 28.96, 29.26, 29.42, 30.01, 30.11, 30.25, 30.81, 31.58, 31.79, 46.15, 52.14, 60.20, 60.68, 68.09, 68.79, 123.97, 124.27, 124.44, 124.62, 124.98, 125.88, 126.28, 128.09, 128.27, 129.64, 129.75, 129.85, 131.16, 131.47, 133.04, 134.34, 139.45, 140.07, 145.68, 145.78, 146.94, 147.27, 147.70, 150.06, 184.67, 186.02; IR (KBr): v = 2943, 2858, 2195, 1631, 1512, 1486, 1473, 1443, 1381, 1354, 1307, 1273, 1253, 1168, 1143, 1096, 1011, 779, 632; HR-MS (FAB+): calc.: C40H53CIN3Pd [M-CI]+= 716.2963, found:
716.3002 Example 10:
1H NMR (300 MHz, CDCI3): 6 = 1.49 (s, 9 H, CH3), 1.71 (s, 9 H, CH3), 3.57 (s, 3 H, CH3), 3.73 (m, 4 H, CH2); 13C NMR (75 MHz, CDCI3): 6 = 30.23, 30.72, 39.22, 47.71, 50.57, 53.64, 56.97, 77.65, 183.1; IR (KBr): v = 3444, 2980, 2218, 1630, 1530, 1466, 1371, 1324, 1287, 1200, 1136, 620; HRMS (FAB+) C13H24N3Pd [M-HCl2]+: calc.
328.1011, found: 328.1005 Example 11:
1H NMR (300 MHz, CD2Cl2): 6 = 1.19 (d, 3 H, J= 6.8 Hz, -CH3), 1.26 (d, 3 H, J=
6.7 Hz, -CH3), 1.45 (s, 9 H, -CH3), 1.65 (s, 9 H, -CH3), 3.38-3.79 (m, 4 H, -CH2-), 5.56 (m, 1 H, J= 6.7 Hz, -CH-); 13C NMR (75 MHz, CD2Cl2): 6 = 18.55, 19.27, 29.01, 29.44, 40.68, 46.02, 52.17, 55.79; IR (KBr): v = 2979, 2936, 2876, 2217, 1635, 1504, 1454, 1400, 1369, 1322, 1285, 1235, 1197, 1111, 806, 622, 594, 523; HR-MS (FAB+): calc.:
C15H29CIN3Pd [M-CI]+= 392.1085, found: 392.1074 Example 12:
1H NMR (300 MHz, CD2Cl2): 6 = 0.98-2.12 (m, 10 H, -CH2-), 1.45 (s, 9 H, -CH3), 1.66 (s, 9 H, -CH3), 3.39-3.77 (m, 4 H, -CH2-), 5.06 (m, 1 H, -CH-); 13C NMR (75 MHz, CD2Cl2): 6 = 24.42, 24.53, 29.00, 29.14, 29.45, 30.07, 41.97, 45.97, 55.83, 59.82, 179.92; IR (KBr): v = 2918, 2933, 2856, 2216, 1631, 1502, 1451, 1371, 1313, 1283, 1263, 1247, 1225, 1195, 1088, 1031, 804, 622; HR-MS (FAB+): calc.:
C18H33CIN3Pd [M-CI]+= 432.1398, found: 432.1410 Example 13:
1H NMR (300 MHz, CDCI3): 6 = 2.35 (s, 3 H, CH3), 2.58 (s, 3 H, CH3), 3.66 (s, 3 H, CH3), 4.02 (m, 4 H, CH2), 7.14 (m, 1 H, ArH), 7.19 (m, 1 H, ArH), 7.27 (m, 2 H, ArH), 7.30 (m, 2 H, ArH) ppm; 13C NMR (75 MHz, CDCI3): 6 = 19.37, 19.75, 38.20, 50.94, 52.10, 77.45, 127.56, 127.74, 129.31, 130.62, 130.99, 131.03, 131.13, 133.06, 135.22, 138.96, 141.41, 186.60; IR (KBr): v = 3431, 2202, 1632, 1549, 1487, 1458, 1413, 1319, 1273, 1114, 781, 730, 617; HRMS (FAB+) C19H19N3C13Pd [M-C1]+: calc.
499.9679, found: 499.9636 Example 14:
(Mixture of diastereoisomers); 1H NMR (500 MHz, CDCI3): 6 = 1.45-2.02 (m; 8 H, CH2), 2.01 (s, -CH3), 2.03 (s, -CH3), 2.27 (s, -CH3), 2.29 (s, -CH3), 2.52 (s, -CH3), 2.54 (s, -CH3), 3.32 (td, J= 12.7, 3.3 Hz, -CH2-), 5.07 (m, -CH2-), 5.14 (m, -CH2-), 6.85-6.91 (m, ArH), 7.08-7.10 (m, ArH), 7.16-7.26 (m, ArH); IR (KBr): v = 2939, 2856, 2196, 1631, 1519, 1443, 1381, 1307, 1273, 1254, 782, 631, 577; HRMS (FAB+) C24H29N3CIPd [M-HCl]: calc. 500.1085, found: 500.1060 Example 15:
(Mixture of diastereoisomers, major isomer); 1H NMR (500 MHz, CDCI3): 6 = 0.00 (d, J
= 6.6 Hz, 3 H, -CH3), 0.88 (d, J = 6.6 Hz, 3 H, -CH3), 1.09 (d, J = 6.6 Hz, 6 H, -CH3), 1.09 (d, J = 6.6 Hz, 6 H, -CH3), 1.26 ¨ 1.73 (m, 25 H, -CH2-), 1.59 (d, J =
6.6 Hz, 6 H, -CH3), 1.68 (m, 2 H, -CH2-), 1.97 (m, 1 H, -CH2-), 2.22 (m, 1 H, -CH2-), 2.59 (m, J = 6.6 Hz, 2 H, -CH-), 2.84 (m, J = 6.6 Hz, 1 H, -CH-), 3.54 (m, 1 H, -CH-), 3.83 (m, 1 H, -CH2-), 4.29 (m, 1 H, -CH2-), 4.83 (m, 1 H, -CH-), 5.24 (m, 1 H, -CH-), 6.99 (d, J
= 7.7 Hz, 1 H, ArH), 7.05 ( d, J = 7.7 Hz, 2 H, ArH), 7.17 (d, J = 7.7 Hz, 1 H, ArH), 7.25 ¨ 7.33 (m, 5 H, ArH), 7.37 (d, J = 6.8 Hz, 2 H, ArH); 13C NMR (125 MHz, CDCI3): 6 = 22.83 (2 C), 23.09 (2 C), 23.67, 24.60, 25.36 (2 C), 26.52, 26.58, 26.72 (2 C), 26.94 (2 C), 27.07, 27.08, 27.11, 27.22, 27.45 (2 C), 28.71, 28.80, 29.65 (2 C), 30.83, 32.50, 52.72, 60.84, 68.75, 123.50 (2 C), 124.11, 126.06, 128.04 (2 C), 129.54, 129.56 (2 C), 129.61, 130.74, 134.22, 139.64, 145.34, 145.51 (2 C), 140.34, 186.39.

11.1.2 Synthesis NHC-Au(I) complexes General procedure for the synthesis of NHC-Au(I) complexes 5 In a typical protocol the (isonitrile)-Au(I) complex (132 pmol) and the 2-(chloroethyl)ammonium chloride (396 pmol) were suspended in absolute DCM.
Triethylamine (0.5 ml, 6.81 mmol) was added. The mixture was stirred for 96 h at am-bient temperature. After this all the volatiles were removed under reduced pressure and the solid was dissolved in DCM (10 m1). The solution was extracted with a saturated 10 solution of NH4CI (20 m1). The organic layer was dried with Na2SO4 and the solvent was removed under reduced pressure. The crude products were purified by column chromatography (Si02, mixtures of petrol ether and ethyl acetate; examples 15 and 18:
petrolether/ethyl acetate, 2/1; example 16: petrolether/ethyl acetate, 5/1 and example 17: petrolether/ethyl acetate, 1/1). All the complexes of examples 15 to 18 listed below 15 in table!! are air and moisture stable compounds and can be stored at ambient tem-perature without decomposition.
Table 11 R1NN'R2 (I-A.2.1) with M being AuCI
Au I
Cl Ex. R1 R3 R2 R7 yield / material property 16 2,4,6-trimethylphenyl H isopropyl H 45%, colourless solid 17 2,4,6-trimethylphenyl H 1-adamantyl H 50%, colourless solid 18 2,6-diisopropylphenyl H isopropyl H 80%, colourless solid 19 tert-butyl H isopropyl H 80%, colourless solid The physicochemical data of the complexes of the examples 16 to 19 are listed below:
Example 16:
R( petrol ether/ethyl acetate 2/1)= 0.28; 1H NMR (300 MHz, CD2Cl2): 6 = 1.28 (d, 6 H, J= 6.8 Hz, -CH3), 2.17 (s, 6 H, -CH3), 1.26 (s, 3 H, -CH3), 3.72 (s, 4 H, -CH2-), 4.79 (m, 1 H, J= 6.8 Hz, -CH-), 6.92 (s, 2 H, ArH); 13C NMR (75 MHz, CD2Cl2): 6 =
17.01, 19.63, 20.09, 42.34, 49.34, 50.89, 128.68, 134.64, 135.19, 138.03, 191.54; IR (KBr):
v =
2968, 1609, 1506, 1456, 1369, 1344, 1322, 1276, 1263, 1202, 1161, 1099, 1058, 1021, 862, 804, 613, 604, 582; HR-MS (FAB+): calc.: C15H23CIN2Au [M+H+]+= 463.1215, found: 463.1194 Example 17:
R( petrol ether/ethyl acetate 5/1)= 0.22; 1H NMR (500 MHz, CD2Cl2): 6 = 1.69 (s, 6 H), 2.16 (s, 9 H), 2.26 (s, 3 H), 2.38 (s, 6 H), 3.60 (m, 2 H, -CH2-), 3.89 (m, 2 H, -CH2-), 6.92 (s, 2 H, ArH); 13C NMR (75 MHz, CD2Cl2): 6 = 18.17, 21.27, 30.42, 36.37, 43.75, 46.86, 49.30, 57.43, 129.79, 136.12, 137.20, 139.01, 192.76; IR (KBr): v =
2909, 2851, 1631, 1543, 1494, 1449, 1360, 1312, 1272, 1192, 1142, 1103, 1036, 852, 817, 674, 607, 581 Example 18:
1H NMR (300 MHz, CD2Cl2): 6 = 1.19 (d, 6 H, J= 7.0 Hz, -CH3), 1.29 (d, 12 H, J= 6.8 Hz, -CH3), 2.86 (m, 2 H, J= 6.9 Hz, -CH-), 3.74 (s, 4 H, -CH2-), 4.81 (m, 1 H, J= 6.8 Hz, -CH-), 7.19 (d, 2 H, J= 7.8 Hz, ArH), 7.38 (m, 1 H, ArH); 13C NMR (75 MHz, CD2Cl2):
6 = 19.67, 23.31, 23.91, 27.72, 42.34, 50.92, 51.98, 123.74. 128.89, 134.09, 146.23, 192.18; 15N NMR (600 MHz, CD2Cl2, urea): 6 = 130.29, 146.50; IR (KBr): v =
2964, 2926,2867, 1631, 1502, 1460, 1385, 1367, 1318, 1274, 1236, 1192, 1163, 1111, 1059, 1019, 808, 763, 601; HR-MS (FAB+): calc.: C18H29CIN2Au [M+H+]+= 505.1685, found:
505.1652 Example 19:
R( petrol ether/ethyl acetate // 2/1)= 0.18; 1H NMR (300 MHz, CD2Cl2): 6 =
1.19 (d, 6 H, J= 6.8 Hz; -CH3), 1.57 (s, 9 H, -CH3), 3.4 (dd, J= 11.4, 8.9 Hz, -CH2), 3.64 (dd, J= 11.4, 8.9 Hz, -CH2), 4.88 (m, J= 6.8 Hz, -CH-); 13C NMR (125 MHz, CD2Cl2): 6 =
20.61, 30.92, 41.92, 47.40, 53.65, 56.06, 191.32; IR (KBr): v = 2968, 2875, 1494, 1450, 1397, 1366, 1328, 1282, 1235, 1202, 1117, 955, 711, 676, 610, 521, 436; HR-MS
(FAB+): calc.: C10H21CIN2Au [M+H+]+= 401.1059, found: 401.1005 11.1.3 General procedure for the synthesis of NHC-Pt(II) complexes In a typical protocol the cis-(isonitrile)-Pt(11) complex (156 pmol) and the 2-(chloroethyl)ammonium chloride (200 pmol) were suspended in absolute DCM.
Triethylamine (0.25 ml, 3.4 mmol) was added. The mixture was stirred for 72 h at am-bient temperature. After this all the volatiles were removed under reduced pressure and the solid was dissolved in DCM (10 m1). The solution was extracted with a saturated solution of NH4CI (20 m1). The organic layer was dried with Na2504 and the solvent was removed under reduced pressure. All the complexes of examples 19 and 20 listed below in table III are air and moisture stable compounds and can be stored at ambient temperature without decomposition.
Table III

R1z (l-A.2.1) with M being PtC12(CNR1) CI
R1---"N ------ I
Cl Ex. R1 R3 R2 R7 yield / material property 20 2,6-diisopropylphenyl H isopropyl H 63%, colourless solid 21 2,6-diisopropylphenyl H cyclohexyl H 70%, colourless solid The physicochemical data of the complexes of the examples 20 and 21 are listed be-low:
Example 20:
1H NMR (500 MHz, CD2Cl2): 6 = 1.04 (d, 3 H, J= 6.7 Hz, -CH3), 1.06 (d, 3 H, J=
6.7 Hz, -CH3), 1.13 (d, 3 H, J= 6.7 Hz, -CH3), 1.19 (d, 6 H, J= 6.9 Hz, -CH3), 1.2 (d, 6 H, J= 6.9 Hz, -CH3), 1.34 (d, 6 H, J= 6.6 Hz, -CH3), 1.43 (d, 3 H, J= 6.7 Hz, -CH3), 2.88 (m, 1 H, J= 6.7 Hz, -CH-), 3.24 (m, 3 H, -CH-), 3.72-3.98 (m, 4 H, -CH2-), 5.50 (m, 1 H, J= 6.6 Hz, -CH-), 7.16 (m, 3 H, ArH), 7.27 (d, 1 H, J= 7.6 Hz, ArH), 7.39 (m, 2 H, ArH); 130 NMR (125 MHz, CD2Cl2): 6 = 20.24, 20.58, 23.03, 23.11, 23.47, 23.93, 26.74, 26.88, 28.89, 29.23, 29.92, 43.24, 52.24, 124.23, 124.60, 125.63, 130.19, 130.68, 134.68, 146.15, 146.47, 148.62, 173.14; 195Pt NMR (498 MHz, CD2Cl2, Na2PtC14): 6 = -3669.80;
HR-MS (FAB+): calc.: C31 H4502N3Pt [M-CI]+= 689.2950, found: 689.2914.
Example 21:
1H NMR (600 MHz, CD2Cl2): 6 = 1.08 (d, 3 H, J= 6.8 Hz, -CH3), 1.10 (d, 3 H, J=
6.8 Hz, -CH3), 1.17 (d, 3 H, J= 6.8 Hz, -CH3), 1.23 (d, 6 H, J= 6.8 Hz, -CH3), 1.25 (d, 6 H, J=
6.8 Hz, -CH3), 1.36 (t, 1 H, J= 7.3 Hz, -CH2-), 1.38 (d, 3 H, J= 6.8 Hz, -CH3), 1.46-1.58 (m, 3 H, -CH2-), 1.67 (qd, 1 H, J= 12.1, 3.2 Hz, CH3), 1.74 (d, 1 H, J= 14.3 Hz, -CH2-), 1.91 (t, 3 H, J= 14.3 Hz, -CH2-), 2.34 (m, 1 H, -CH2-), 2.93 (m, 1 H, J= 6.8 Hz, -CH-), 3.26 (m, 2 H, J= 6.8 Hz, -CH-), 3.32 (m, 1 H, J= 6.8 Hz, -CH-), 3.79-4.03 (m, 4 H, -CH2-), 5.00-5.06 (m, 1H, -CH-), 7.20 (dd, 1 H, J= 7.8, 1.4 Hz, ArH), 7.22 (d, 2 H, J=
7.8, ArH), 7.32 (dd, 1 H, J= 7.8, 1.4 Hz, ArH), 7.43 (t, 1 H, J= 7.8, ArH), 7.44 (t, 1 H, J=
7.8, ArH); 13C NMR (150 MHz, CD2Cl2): 6 = 22.81, 22.92, 23.38, 23.75, 25.41, 25.50, 25.68, 26.57, 26.70, 28.70, 29.05, 29.79, 30.55, 31.36, 44.35, 45.99, 59.68, 124.06,124,30, 124.41, 125.44, 129.98, 130.49, 134.59, 145.93, 146.29, 148.44, 172.84; HR-MS (FAB+): calc.: C34H49C12N3Pt [M-CI]+= 729.3263, found: 729.3265.
11.2. Synthesis of NHC-(transition metal) complexes of the formula I-B.2.1 11.2.1 Synthesis of Au(I)-NHC complexes General procedure:

) Ri i_N7 \N
S I H -----R
Au H3Cõoõ..----........õ.õ...N...... 2 -1"-II
I Y R
I C Au I
Cl Cl (I-B.2.1) M = AuCI
Under an atmosphere of nitrogen (tetrahydrothiophene)AuCI (1.00 equivalent, 50.0 [trnol) was dissolved in absolute DCM (0.10 M) at ambient temperature. The isonitrile (1.05 equivalents) in question was added and the solution was stirred for 5 min. After this, the amine in question (1.50 equivalents) was added and stirring was continued for 36 h. The solvent was removed under reduced pressure and the resulting crude prod-uct was washed with cold pentane (five times, 2 ml. The product was dried under re-duced pressure. Alternatively, the compounds can be purified by column chromatogra-phy using mixtures of petrol ether and ethyl acetate on basic alumina.
Example 22: Chloro(1-cyclohexy1-3-(2,6-diisopropylphenyl)imidazolin-4-on-2-ylidene)gold(1) 7 \
N N
le Au \
CI

1H NMR (500 MHz, CDCI3/C6D6 /4/1): 6 = 1.08 (d, J= 6.9 Hz, 6 H, -CH3), 1.24 (d, J= 6.9 Hz, 6 H, -CH3), 1.42 (m, 5 H, -CH2-), 1.68 (m, 1 H, -CH2-), 1.82 (m, 2 H, -CH2-), 1.97 (m, 2 H, -CH2-), 2.51 (m, J= 6.9 Hz, 2 H, -CH-), 3.94 (s, 2 H, -CH2-, carbene backbone), 4.44 (m, 1 H, -CH-), 7.16 (d, J= 7.8 Hz, 2 H, ArH), 7.37 (t, J= 7.8 Hz, 1 H, ArH); 13C
NMR (125 MHz, CDC13/C6D6 4/1): 6 = 24.26, 24.28, 24.97, 25.10, 29.50, 31.99, 48.59, 63.29, 124.73, 129.24, 131.22, 146.29, 171.84,201.85.
Example 23: Chloro(1-cyclododecy1-3-(2,6-diisopropylphenyl)imidiazolin-4-on-2-ylidene)gold(1) I, N
y 1H NMR (250 MHz, CDC13): 6 = 1.13 (d, J= 6.9 Hz, 6 H, -CH3), 1.21 (d, J= 6.9 Hz, 6 H, -CH3), 1.18 - 1.71 (m, 20 H, -CH2-), 1.94 (m, 2 H, -CH2-), 2.57 (m, J= 6.9 Hz, 2 H, -CH-), 4.06 (s, 2 H, -CH2-, carbene backbone), 4.9 (m, 1 H, -CH-), 7.22 (d, J=
7.7 Hz, 2 H, ArH), 7.44 (t, J= 7.7 Hz, 1 H, ArH).
Example 24: Chloro(3-(2,6-diisopropylpheny1)-1-(1-phenylethypimidazolin-4-on-2-ylidene)gold(1) \r, N,y3.16 .11113 Au el 1H NMR (250 MHz, CDC13): 6 = 1.03 (d, J= 6.9 Hz, 3 H, -CH3), 1.10 (d, J= 6.9 Hz, 3 H, -CH3), 1.27 (d, J= 6.9 Hz, 2 H, -CH3), 1.29 (d, J= 6.9 Hz, 3 H, -CH3), 1.81 (d, J= 7.2 Hz, 3 H, -CH3), 2.43 (m, J= 6.9 Hz, 2 H, -CH-), 3.65 (d, J= 21.2 Hz, 1 H, -CH2-, carbene backbone), 4.03 (d, J= 21.2 Hz, 1 H, -CH2-, carbene backbone), 6.06 (q, J= 7.2 Hz, 3 H, -CH-), 7.2 (m, 8 H, ArH).
11.2.2 Synthesis of Pd(11)-NHC complexes General procedure for the synthesis of Pd(11)-NHC complexes of the formula 1-B.2.1 CD

H R N7N¨R2 Pd(Cl2(CNR1)2) + 1-13C...0N,R2 ¨).-CI---Tdc CI ----N, Ri (1-6.2.1) M = PdC12(CNR1) Under an atmosphere of nitrogen the palladium bis(isonitrile) complex in question (1.00 equivalent, 50.0 mop was dissolved in absolute THF (0.30 M) at ambient temperature.
After this, the amine in question (1.10 equivalents) was added and stirring was contin-5 ued for 7 d. The solvent was removed under reduced pressure and the resulting crude product was washed with cold pentane (five times, 2.00 ml). The product was dissolved in a minimum of DCM and cold pentane was added to induce precipitation of the Pd(II)-NHC complex.
10 Example 25: Compound of the formula I-B.2.1 with R1 = 2,6-diisopropyl, R2 = cyclo-hexyl o, \
,..---\--- CI
i PJ

......
___________________________________ , 1H NMR (250 MHz, CDCI3): 6 = 0.93 (d, J= 6.8 Hz, 3 H, -CH3), 0.96 (d, J= 6.8 Hz, 3 H, -CH3), 1.04 (d, J= 6.8 Hz, 3 H, -CH3), 1.19 (d, J= 6.8 Hz, 6 H, -CH3), 1.21 (d, J= 6.8 Hz, 15 6 H, -CH3), 1.4 (d, J= 6.8 Hz, 3 H, -CH3), 1.10¨ 2.05(m, 10 H, -CH2-), 2.54 (m, 1 H, -CH-), 3.13 (m, 3 H, -CH-), 4.32 (m, 2 H, carbene backbone), 5.22 (m, 1 H, -CH-), 7.17 (m, 2 H, ArH), 7.44 (m, 4 H, ArH).
By recrystallization of the title compound from DCM/petrol ether, the compound of the 20 following formula 0, 7 ____________ \
O
CI

Cl' 1 H 0 was obtained.
11.3. Synthesis of NHC-(transition metal) complexes of the formula 1-C.2.1 11.3.1 General synthesis of Au(I)-NHC complexes Under an atmosphere of nitrogen an chloroimidiazolin-4-on-2-ylidene)gold(I) complex in question (50.0 mg, 77.6 pmol, 1 equivalent) was dissolved in absolute THF.
The mix-ture was cooled to -78 C and lithium bis(trimethylsilyl)amide (0.14 M in THF, 610 pl, 1.1 equivalents) was added. The mixture was stirred at -78 C for 30 min prior to add-ing the electrophile (1.1 equivalents). The mixture was allowed to warm up to ambient temperature and stirring was continued for 30 min. After this, the solvent was removed and the resulting crude product was washed with pentane (three times, 3 m1).
The product was dissolved in absolute DCM and filtrated through a pad of celite to remove the LiCI. The solvent was removed under reduced pressure and the resulting solids were stored under an atmosphere of nitrogen at -32 C.
Example 26: Chloro(4-((tert-butyldiphenylsilypoxy)-1-cyclododecyl-3-(2,6-diisopropylpheny1)-imidazol-2-ylidene)gold(1) Fh13.1-µ1.4_ =
s, Ny N
Aiu a According to the general procedure, the title compound was prepared using tert-butyl diphenylchlorosilane as electrophile.
1H NMR (250 MHz, CD2Cl2): 6 = 0.85 (s, 9 H, -CH3), 1.09 (d, J= 6.9 Hz, 6 H, -CH3), 1.26 (d, J= 6.9 Hz, 6 H, -CH3), 0.95-1.79 (m, 22 H, -CH2-), 2.42 (m, J= 6.9 Hz, 2 H, -CH-), 4.63 (m, J= 6.8 Hz, 1 H, -CH-), 5.59 (s, 1 H, =CH), 7.31 (m, 6 H, ArH), 7.45 (m, 7 H, ArH).
Example 27: Chloro(4-(benzoyloxy)-1-cyclododecy1-3-(2,6-diisopropylpheny1)-imidazol-2-ylidene)gold(I) 0 it O \
NIyN_..Cz, 41), Aiu CI
According to the general procedure, the title compound was prepared using benzoyl chloride as electrophile.
1H NMR (250 MHz, C6D6): 6 = 0.98 (d, J= 6.8 Hz, 6 H, -CH3), 1.33 (d, J= 6.8 Hz, 6 H, -CH3), 1.05 - 1.92 (m, 22 H, -CH2-), 2.62 (m, J= 6.8 Hz, 2 H, -CH-), 5.17 (m, J= 6.5 Hz, 1 H, -CH-), 6.76 (t, J= 7.7 Hz, 2 H, ArH), 6.91 (t, J= 7.5 Hz, 1 H, ArH), 7.03 (d, J=
7.7 Hz, 2 H, ArH), 7.19 (m, 2 H, ArH, =CH), 7.68 (m, 2 H, ArH).
Example 28: Chloro(4-((((4,5-dimethoxy-2-nitrobenzypoxy)carbonyl)oxy)-1-cyclododecyl-3-(2,6-diisopropylpheny1)-imidazol-2-ylidene)gold(1) \c) ght NO2 0_...ip (:)\_ =Ny N
Au CI
According to the general procedure, the title compound was prepared using 4,5-dimethoxy-2-nitrobenzylchloroformate as electrophile.
1H NMR (250 MHz, CDCI3): 6 = 1.05 (d, J= 6.8 Hz, 6 H, -CH3), 1.26 (d, J= 6.8 Hz, 6 H, -CH3), 1.02 - 1.88 (m, 22 H, -CH2-), 2.32 (m, J=
6.8 Hz, 2 H, -CH-), 3.83 (s, 3 H, -CH3), 3.93 (s, 3 H, -CH3), 5.58 (s, 2 H, -CH2-), 6.79 (s, 1 H, =CH), 7.16 (s, 1 H, ArH), 7.2 (d, J= 7.8 Hz, 2 H, ArH), 7.44 (t, J= 7.8 Hz, 1 H, ArH), 7.68 (s, 1 H, ArH).
111 Catalytic activity of the Pd(II)-NHC complexes 111.1 General procedure for Suzuki-Miyaura reactions B(OH)2 O X
+ H3C le CH3 [Pd] lel )...

X = Cl or Br [Pd] = Pd catalyst of the formula I-A.2.1 There are two protocols for this reaction dependent on the phenyl halide used as sub-strate.
Procedure for chlorobenzene as substrate Under an atmosphere of nitrogen, the Pd(II)-NHC complex of example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 [1 mol%], 2,5-dimethylphenylboronic acid (1.20 mmol) and chlorobenzene(1.00 mmol) were dissolved in ethanol (2 ml). The mixture was stirred for 5 min and the base potassium tert-butanolate (1.00 mmol) was added. The solution was stirred for 12 h. The yield was determined by GC using dodecane (1.00 mmol) as internal standard. The results are summarized in Table IV.
Procedure for bromobenzene as substrate Under an atmosphere of nitrogen, the Pd(II)-NHC complex of example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 [0.1 mol%], the 2,5-dimethylphenylboronic acid (2.40 mmol) and bromobenzene (2.00 mmol) were dissolved in ethanol (4 ml). The mixture was stirred for 5 min and the base potassium tert-butanolate (2.00 mmol) was added. The solution was stirred for 12 h. The yield was determined by GC using dodecane (1.00 mmol) as internal standard. The results are summarized in table IV.
Table IV:
Example catalyst from example Yield (%) starting from Yield (%) starting from chlorobenzene bromobenzene 33 3 3 _ Example catalyst from example Yield (%) starting from Yield (%) starting from chlorobenzene bromobenzene 111.2 General procedure for the Sonogashira reaction Under an atmosphere of nitrogen the catalyst of example 15 (2 mol%) was suspended in ethanol (1.00 m1). Bromobenzene (1.00 mmol, 102 pl) and 1-hexyne (1.50 mmol, 173 pl) were added. Finally, KOtBu (1 mmol, dissolved in 1.00 ml ethanol) was added and the mixture was stirred for 12 h at ambient temperature. The solvent used was techni-cal grade ethanol without prior degassing. After this, ammonium chloride (saturated solution, 2.00 ml), ethyl acetate (4.00 ml) and dodecane (1.00 mmol, 226.2 pl) were added. The organic layer was dried with Na2SO4 and analysed by GC. Yield of hex-1-ynylbenzene: 55%.
IV Synthesis of NHC-(transition metal) complexes of the formula 1-E
IV.1 Synthesis of acyclic gold complexes of the formula (VI) Route a) R\ I R11N R3 N 0 __ KR8 \ R11 _,...
H
R2N./<R11 +
0 AuR 1 R

¨
I

Au Cl(6) I
CI
(7) (8) R1, R2, R3, R8, R1 and R" have the aforementioned meanings.
In a typical protocol, 1-2 equiv. of the amine (6) were added to a solution of an iso-5 cyanogold(I) complex (7) in dichloromethane. The mixture was stirred at room tempera-ture for 1-3 days. The solvent was removed under reduced pressure. If necessary, the crude product was purified by column chromatography on silica gel (dichloromethane as eluent).
10 Route b) The synthesis of the acyclic gold(I) carbene (8) can also be achieved in a one-pot pro-cedure, starting from (tetrahydrothiophene)AuCI ((tht)AuCI) in dichloromethane. After addition of the R1-NC, the mixture was stirred at room temperature for 1 h and the amine (6) was added subsequently.
All the complexes are air and moisture stable and can be stored at room temperature without decomposition.
Example 53: Chloroacyclododecy1(2,2-dimethoxyethypamino{[2,6-diisopropylphenyl]amino} methylidene)aurate H,C 'CH, \o CH, 0 H,C ---H
N N
0 Au A
CI
H,C
CH, The title compound was prepared according to the general procedure using 100 mg of (238 mmol) 2,6-diisopropylphenylisocyanogold(I) chloride and 71.2 mg (250 mmol) of N-(2,2-dimethoxyethyl)cyclododecanamine in 5 ml dichloromethane. The reaction mix-ture was stirred at room temperature for 24 h and purified by column chromatography to afford a colourless crystaline solid; yield: 151 mg (219 mmol, 92 %); 1H-NMR (300 MHz, CD2Cl2): 6 = 1.18 (d, J= 6.9 Hz, 6H, CH3), 1.24-1.61 (m, 19H), 1.35 (d, J
= 6.9 Hz, 6 H, CH3), 3.08 (sept, J= 6.9 Hz, 2H, CH), 3.47 (s, 6H, OCH3), 3.56 (d, J=
4.8 Hz, 2H, CH2N), 4.51 (t, J = 4.8 Hz, 1H, CH(OCH3)2), 7.21 (d, J = 7.4 Hz, 2 H, ArH), 7.50 (t, J = 7.4 Hz, 1H, ArH); 13C-NMR (75 MHz, CD2Cl2): 6 = 22.55 (t, 2C), 22.68 (t, 2C), 23.29 (q, 2C), 23.59 (q, 2C), 24.14 (t, 2C), 24.62 (t, 2C), 24.67 (t, 1C), 28.68 (d, 2C), 29.51 (t, 1C), 48.75 (t, 2C), 53.83 (q, 2C), 64.83 (d, 1C), 105.01 (d, 1C), 124.14 (d, 2H), 129.47 (d, 1C), 135.89 (s, 1C), 146.99 (s, 2C), 198.34 (s, 1C); IR (KBr): v =
3540, 3268, 2931, 2864, 1592, 1537, 1469, 1445, 1414, 1384, 1362, 1331, 1240, 1197, 1162, 1119, 1056, 1016, 801, 759 cm-1; HR-MS (FAB+): m/z = 690.3202, calcd. for C29H50AuCIN202[M]: 690.3226, m/z = 655.3509. calcd. for C29H50AuN202[M- Cl-]+:
655.3538.
IV.2 Synthesis of acyclic-(palladium or platin) complexes Ri \ N ,R3 \ R3 11 -I- H
R2...--N,...,..õ..."<o..-R CI¨M =N Ri ¨3.-RiN I\IR2 I
R8 (6) Cl CI NA __ _N R1 I
(9) (10) M is Pd or Pt;
R1, R2, R3, R8, R1 and R11 are as defined above.
In a typical protocol, cis-(isonitrile)2-MeCl2 complex (9) and 1 equiv. of the amine (6) were stirred in dry THF under an atmosphere of nitrogen for 2-5 days at room tem-perarture. Complete consumption of the starting material was monitored by the shift of the IR stretching frequencies of the isonitrile ligands. The solvent was removed under reduced pressure and the crude product was dissolved in a minimum amount of di-chloromethane and covered with a layer diethyl ether, inducing crystallization of the acyclic carbene complex (10) as colourless crystals. The crystals were filtered off, washed with n-pentane or diethyl ether and dried under reduced pressure. The com-plexes are air and moisture stable and can be stored at room temperature without de-composition.
Example 54 H3C ,CH3 CH \ 0 H
le cNirN---.0 Pd I \C CH3 H3C CI \\`N
CH

H3C =

The title compound was prepared according to the typical protocol above using 70 mg of (0.31 mmol) cis-[PdC12(2,6-diisopropylphenyl isonitrile)2 and 58.1 mg (0.31 mmol) of N-(2,2-dimethoxyethyl)cyclohexanamine in 8 ml dry of THF. Yield: 204 mg (276 mmol, 89 %); 1H-NMR (500 MHz, CD2Cl2): 6 = 0.93 (d, J= 6.9 Hz, 3H, CH3), 1.08 (d, J=
6.9 Hz, 3H, CH3), 1.13 (d, J= 6.9 Hz, 3H, CH3), 1.23 (d, J= 6.9 Hz, 6H, CH3), 1.24 (d, J =
6.9 Hz, 6H, CH3), 1.52 (d, J= 6.9 Hz, 3H, CH3), 1.52-1.72 (m, 6H), 1.82 (m, 1H), 1.96 (m, 3H), 2.45 (m, 1H), 2.87 (sept, J= 6.9 Hz, 1H, CH), 3.06 (sept, J= 6.9 Hz, 2H, CH), 3.51 (s, 3H, CH3), 3.60 (s, 3H, CH3), 3.71 (d, J= 4.7 Hz, 2H, CH2), 3.88 (sept, J= 6.9 Hz, 1H, CH), 4.57 (t, J = 4.7 Hz, 1H, CH), 7.11 (m, 1H, ArH), 7.23 (m, 2H, ArH), 7.44 (m, 3H, ArH), 8.71 (bs, 1H, NH); 13C-NMR (500 MHz, CD2Cl2): ; 20.88, 22.56, 22.97 (2C), 23.35 (2C), 25.63, 25.70, 25.88 (2C), 26.04 (2C), 26.08 28.84, 29.72, 29.98 (2C), 31.36, 31.60, 50.17, 55.34, 57.01, 68.37, 105.59, 123.05, 124.1, 125.1, 129.77, 131.18, 134.65, 145.85, 146.15 (2C), 149.38, 191.16; IR (KBr): v = 3447, 3262, 2964, 2932, 2863,2185, 1665, 1630, 1591, 1543, 1463, 1418, 1386, 1360, 1331, 1142, 1119, 1060, 800, 750 cm-1; HR-MS (FAB+): m/z= 702.3038, calcd. for C36H55CIN302Pd [M- Cl-]:
702..3028, rniz =667.3921, calcd. for C36H55N302Pd [M- 2CI- ]: 667.3329.
IV.3 Synthesis of complexes of the formula I-E
In a typical protocol, the acyclic Au(I)-complex (8) and Pd(II)- or Pt(II) complex (10), respectively, were dissolved in dichloromethane. HCI (4N in HCI) was added and the mixture was stirred at room temperature for 12 h. The solvent was removed under re-duced pressure. If necessary, the crude product was purified by column chromatogra-phy on silica gel (dichloromethane as eluent) to afford the NHC complexes as crysta-line solids in quantitave yields. All the complexes are air and moisture stable and can be stored at room temperature without decomposition.
Example 55: Chloro{1-cycloocty1-342,6-diisopropylyl)pheny1]-1,3-dihydro-2H-imidazol-2-ylid-ene}aurate H,C CH3 ______________________________ is NyN
Au CI
H3C cH3 1 00 mg (0.16 mmol) of chloroacycloocty1(2,2-di-methoxyethypamino{[2,6-diisopropylphenyl]amino}methyl-idene)aurate and 0.25 ml of HCI (4N in dioxane) in 5 ml of dichloromethane were stirred at room temperature for 12 h. Evaporation of the solvent afforded the title compound as a colourless crystaline solid; yield:
90.0 mg (0.16 mmol, >99%); 1H NMR (300 MHz, CD2Cl2): 6 = 1.12 (d, J= 6.9 Hz, 6H), 1.28 (d, J
= 6.9 Hz, 6H), 1.38¨ 1.96(m, 10H), 2.02¨ 2.18(m, 4H), 2.33 (sept, J= 6.9 Hz, 2H), 5.01 (quin, J= 6.9 Hz, 1H), 6.95 (d, J= 1.9 Hz, 1H), 7.24 (d, J= 1.9 Hz, 1H), 7.31 (d, J
= 7.8 Hz, 2H), 7.49 (t, J = 7.8 Hz, 1H);13C NMR (75 MHz, CD2Cl2): 6 = 24.54 (q, 2C), 24.62 (q, 2C), 24.91 (t, 2C), 26.35 (t, 1C), 27.22 (t, 2C), 28.97 (d, 2C), 34.78 (t, 2C), 62.72 (d, 1C), 118.27 (d, 1C), 123.94 (d, 1C), 124.66 (d, 2C), 130.91 (d, 1C), 146.48 (s, 2C), 147.07 (s, 1C), 172 (s, 1C); IR (KBr): v = 3433, 2961, 2925, 1865, 1544, 1471, 1459, 1423, 1411, 1385, 1364, 1307, 1254, 1194, 1120, 1058, 873, 807, 765, 740;
HR-MS (FAB+): m/z= 570.2086, calcd. for C23H34AuCIN2[M]: 570.2076.
IV.4 Synthesis of compounds of the formula I-F with M being Au-CI
EWG---\/R4 &R8 iNN----R2 (I-F) R
Au I
Cl R1, R2, R4, R7, R8 and EWG have one of the meanings given above.
Method A: Under an atmosphere of nitrogen the [AuCl(isonitrile)] (1.00 equivalent) complex was dissolved in absolute DCM and the amine (1.50 equivalents) was added.
The mixture was stirred for 48 h and the solvent was removed under reduced pressure.
The resulting solid was washed with petrol ether to remove the residual amine.
Altema-tively, the crude products can be purified by column chromatography using silica and mixtures of petrol ether/ethyl acetate (5:1).
Method B: Under an atmosphere of nitrogen the [AuCl(tht)] (1.00 equivalent) (tht = tet-rahydrothiophene) was dissolved in absolute DCM and the isonitrile (1.00 equivalent) was added. The mixture was stirred for 5 min at RT and the amine (1.50 equivalents) was added. The mixture was stirred for 48 h at RT and the solvent was removed under reduced pressure. The resulting solid was washed with petrol ether to remove the re-sidual amine. Alternatively, the crude products can be purified by column chromatogra-phy using silica and mixtures of petrol ether/ethyl acetate (5:1).
Example 56: (1-Cyclododecy1-3-(2,6-diisopropylpheny1)-4-(2-methoxy-2-oxoethyl)-imidazolidin-2-ylidene)gold(1) chloride iPr) ______________ \
.i Au Pr 1 CI
Colourless solid, 80.0 mg, 114 pmol, 38%;
1H NMR (301 MHz, CD2Cl2) 6= 1.17 (d, J=6.8 Hz, 3 H, -CH3), 1.19 (d, J=6.8 Hz, 3 H, -CH3), 1.21 (d, J=6.8 Hz, 3 H, -CH3), 1.30 (d, J=6.8 Hz, 3 H, -CH3), 1.14-1.84 (m, 22 H, -CH2-), 2.67 (m, J=6.8 Hz, 1 H, -CH-), 2.92 (m, J=6.8 Hz, 1 H, -CH3), 3.32 (dd, J=
11.5, 10.5 Hz, 1 H, -CH2-), 3.48 (s, 3 H, -OCH3), 3.99 (d, J= 11.2 Hz, 1 H, -CH2-), 4.27 (m, 1 H, -CH-), 4.63 (m, 1 H, -CH-), 7.15 (m, 2 H, ArH), 7.34 (t, J=7.7 Hz, 1 H, ArH);
13C NMR (75 MHz, CD2Cl2) 6= 22.49 (t), 22.59 (t), 22.95 (t), 23.24 (t), 23.34 (t), 23.46 (q), 24.10 (q), 24.24 (t), 24.41 (t), 24.66 (t), 24.95 (t), 25.47 (q), 26.30 (q), 28.62 (t), 28.84 (d), 29.15 (d), 29.25 (t), 37.93 (t), 50.54 (t), 52.36 (q), 55.92 (d), 61.41 (d), 124.99 (d), 125.36 (d), 130.30 (d), 133.20 (s), 147.83 (s), 148.34 (s), 170.55 (s), 194.45 (s, carbene carbon atom).
Example 57: (1-Cyclododecy1-4-(2-methoxy-2-oxoethyl)-3-(2-(trifluoromethyl)pheny1)-imidazolidin-2-ylidene)gold(1) chloride CF3 __\
. NyN.-_,,C3 Colourless solid, 115 mg, 167 pmol, 56%; 1H NMR (300 MHz, CD2Cl2) 6= 1.06-1.83 (m, 22 H, -CH2-), 2.50 (m, 2 H, -CH2-), 3.49 (m, 1 H, -CH2-), 3.52 (s, 3 H, -CH3), 3.90 (t, J=
11.0 Hz, 1 H, -CH2-), 4.55 (m, 1 H, -CH-), 4.64 (m, 1 H, -CH-), 7.41 (d, J=
7.7 Hz, 1 H, ArH), 7.54 (m, 1 H, ArH), 7.63 (t, J=7.7 Hz, 1 H, ArH), 7.72 (d, J=7.7 Hz, 1 H, ArH); IR
5 (KBr) v=
2935, 2862, 1738, 1605, 1585, 1500, 1459, 1438, 1316, 1266, 1207, 1174, 1130, 1062, 1037, 999, 773, 645, 599 Example 58: (1-Cyclododecy1-4-(2-methoxy-2-oxoethyl)-3-(naphthalen-2-ypimidazolidin-2-ylidene)gold(1) chloride .---0 4k. NyN,Cj Au CI
Colourless solid, 149 mg, 223 pmol, 74%; 1H NMR (300 MHz, CD2Cl2) 6= 1.10-1.87 (m, 22 H, -CH2-), 2.45 (dd, J= 16.5, 9.0 Hz, 1 H, -CH2-), 2.64 (dd, J= 16.5, 4.3 Hz, 1 H, -CH2-), 3.48 (m, 1 H, -CH2-), 3.50 (s, 3 H, -CH3), 3.97 (t, J= 11.3 Hz, 1 H, -CH2-), 4.71 (m, 1 H, -CH-), 4.83 (m, 1 H, -CH-), 7.46 (m, 2 H, ArH), 7.56 (m, 1 H, ArH), 7.82 (m, 4 H, ArH).

Claims (26)

1. A process for preparing compounds of the general formula (l) where n is = 0 or 1, M is a metal atom containing group, R1 is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl, R2 is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl, wherein R1 and R2 do not both stand for hydrogen, R3 and R4 are independently selected from hydrogen and in each case unsubsti-tuted or substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dialkyl)-amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl)amino, (di-cycloalkyl)amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl)amino, (diheterocycloalkyl)amino, aryl, aryloxy, aryl-thio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl)amino and (dihetaryl)amino, or R3 and R4 together with the carbon atom to which they are bound are C=O, or R3 is a group O-R3a and for n = 0 R4 and R7 stand for the bond equivalent of a double bond between the carbon atoms carrying R4 and R7, respectively or for n = 1 R4 and R5 stand for the bond equivalent of a double bond between the carbon atoms carrying R4 and R5, respectively, where R3a is a group bound to the oxygen via a carbon atom, silicon atom, sulfur atom, phosphorus atom, boron atom or titanium atom, R5, R6, R7 and R8 are independently selected from hydrogen and in each case unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dial-kyl)amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl)amino, (dicycloalkyl)amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkyl-thio, (monoheterocycloalkyl)amino, (diheterocycloalkyl)amino, aryl, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl)amino and (dihetaryl)amino, wherein the two radicals R2 and R8 may also form together with the N atom to which R2 is bound a 3- to 12-membered, unsubstituted or substituted nitro-gen heterocycle which may optionally have 1, 2 or 3 further heteroatoms or heteroatom containing groups independently selected from O, N, NR a and S as ring members, wherein R a is hydrogen, alkyl, cycloalkyl or aryl, or if n = 0, R4 and R7 also may stand for the bond equivalent of a double bond be-tween the carbon atoms carrying R4 and R7, which comprises a1) the reaction of an isonitrile complex of the general formula (II) in which R1 and M have one of the meanings given above, with a compound of the general formulae (III) or (Illa) in which n, R2, R3, R4, R5, R6, R7 and R8 have one of the meanings given above, X- is an anion equivalent, and Y is a leaving group, or if R3 and R4 together with the carbon atom to which they are bound are C=O then Y is a group O-Y a, where Y a is unsubstituted or substi-tuted alkyl, unsubstituted or substituted aryl, unsubstituted or substi-tuted arylcarbonyl or unsubstituted or substituted alkyl carbonyl, and b1) optionally, if R3 and R4 together with the carbon atom to which they are bound are C=O, subjecting the product obtained in step a1) to a further re-action with a compound R3a-Z, where Z is a leaving group, in the presence of a base to obtain a compound of the formula (I) where R3 is a group O-R3a and for n = 0 R4 and R7 stand for the bond equivalent of a double bond be-tween the carbon atoms bound to R4 and R7 or for n = 1 R4 and R5 stand for the bond equivalent of a double bond between the carbon atoms bound to R4 and R5, or a2) the reaction of an isonitrile complex of the general formula II

where R2, R3 and R8 have one of the meanings given above; and R10 and R11 are independently selected from C1-C4-alkyl or R10 and R11 to-gether are linear C2-C4-alkylene which may be substituted by one or more C1-C4 alkyl radicals;
to give an intermediate compound of the formula (VI) in which R1, R2, R3, R8, R10, R11 and M are as defined above and b2) the treatment of the intermediate compound of the formula (VI) with an acid, wherein in compound (I) n is 0, and R4 and R7 stand for the bond equivalent of a double bond between the carbon atoms carrying R4 and R7;
or a3) the reaction of an isonitrile complex of the general formula II
R1¨N.ident.C¨M (II) where R1 and M have one of the meanings given above, with a compound of the general formulae (IIlb) or (IIlc) where R2, R4, R7 and R8 have one of the meanings given above;
X- is an anion equivalent; and EWG is (C(O)R14, C(O)OR14, NO2, S(O)R14 or S(O)2R14, where R14 is hy-drogen, alkyl, cycloalkyl or aryl;
wherein in compound (l) obtained according to variant a3) n is 0 and R3 is CH2-EWG.

2. The process according to claim 1, where n is = 0 or 1;
M is a metal atom containing group;
R1 is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl;
R2 is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl, wherein R1 and R2 do not both stand for hydrogen;
R3 and R4 are independently selected from hydrogen and in each case unsubsti-tuted or substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dialkyl)-amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl)amino, (di-cycloalkyl)amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl)amino, (diheterocycloalkyl)amino, aryl, aryloxy, aryl-thio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl)amino and (dihetaryl)amino, or R3 and R4 together with the carbon atom to which they are bound are C=O, or R3 is a group O-R3a and for n = 0 R4 and R7 stand for the bond equivalent of a double bond between the carbon atoms carrying R4 and R7, respectively or for n = 1 R4 and R5 stand for the bond equivalent of a double bond between the carbon atoms carrying R4 and R5, respectively, where R3a is a group bound to the oxygen via a carbon atom, silicon atom, sulfur atom, phosphorus atom, boron atom or titanium atom;, R5, R6, R7 and R8 are independently selected from hydrogen and in each case unsubstituted or substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dial-kyl)amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl)amino, (dicycloalkyl)amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkyl-thio, (monoheterocycloalkyl)amino, (diheterocycloalkyl)amino, aryl, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl)amino and (dihetaryl)amino, wherein the two radicals R2 and R8 may also form together with the N atom to which R2 is bound a 3- to 12-membered, unsubstituted or substituted nitro-gen heterocycle which may optionally have 1 , 2 or 3 further heteroatoms or heteroatom containing groups independently selected from O, N, NR a and S as ring members, wherein Ra is hydrogen, alkyl, cycloalkyl or aryl, which comprises a1) the reaction of an isonitrile complex of the general formula (II) R1¨N.ident.C¨M
(II) in which R1 and M have one of the meanings given above, with a compound of the general formulae (III) or (IIIa) in which n, R2, R3, R4, R5, R6, R7 and R8 have one of the meanings given above, X- is an anion equivalent, and Y is a leaving group, or if R3 and R4 together with the carbon atom to which they are bound are C=O then Y is a group O-Y a, where Y a is unsubstituted or substi-tuted alkyl, unsubstituted or substituted aryl, unsubstituted or substi-tuted arylcarbonyl or unsubstituted or substituted alkyl carbonyl, and b1) optionally, if R3 and R4 together with the carbon atom to which they are bound are C=O, subjecting the product obtained in step a1) to a further re-action with a compound R3a-Z, where Z is a leaving group, in the presence of a base to obtain a compound of the formula (I) where R3 is a group O-R3a and for n = 0 R4 and R7 stand for the bond equivalent of a double bond be-tween the carbon atoms bound to R4 and R7 or for n = 1 R4 and R5 stand for the bond equivalent of a double bond between the carbon atoms bound to R4 and R5.

3. The process according to claim 1 or 2, wherein R1 and R2 have different mean-ings.

4. The process according to claim 1 or 2, in which M is a Pd(II), Pt(II) or Au(l) con-taining group.

5. The process according to claim 4, in which M is selected from PdCl2(CNR1), PtCl2(CNR1), Au(CNR1) and AuCI, where R1 is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl.

6. The process according to any of the preceding claims, wherein R1 is selected from groups of the formulae IV.1 to IV.5:
in which # represents the bonding site to the nitrogen atom, p is 0 or 1, x is 2 or 3, where, in the case that x is 2, the carbon atom which bears the R i radicals additionally bears 1 hydrogen atom, x1 in the formulae IV.2, IV.3 and IV.4 is 0, 1, 2 or 3, x2 in the formulae IV.2, IV.3 and IV.4 is 0 or 1, with the proviso that the sum of x1 and x2 in the formulae IV.2, IV.3 and IV.4 is 0, 1, 2 or 3, x1 in the formula IV.5 is 0, 1 or 2, x2 in the formula IV.5 is 0 or 1, with the proviso that the sum of x1 and x2 in the formulae IV.5 is 0, 1 or 2, A where present, is a C1-C10-alkylene group which may be interrupted by one or more nonadjacent groups which are selected from -O- and -S-, the R i radicals are each independently selected from C1-C30-alkyl, C1-C30-alkyloxy or C1-C30-alkylthio, wherein the alkyl chain in alkyl, alkyloxy or alkylthio may be interrupted by one or more nonadjacent oxygen atom(s).

7. The process according to any of the preceding claims, wherein R2 is selected from alkyl and cycloalkyl, preferably from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, cyclododecyl and 1-adamantyl.

8. The process according to any of claims 1 to 7, for preparing compounds of the general formulae (l-A.1) or (l-A.2) where M, R1, R2, R5, R6, R7 and R8 have a meaning as defined in any of claims 1 to 7, R3 and R4 are independently selected from hydrogen and in each case unsubsti-tuted or substituted alkyl, alkoxy, alkylthio, (monoalkyl)amino, (dialkyl)-amino, cycloalkyl, cycloalkoxy, cycloalkylthio, (monocycloalkyl)amino, (di-cycloalkyl)amino, heterocycloalkyl, heterocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl)amino, (diheterocycloalkyl)amino, aryl, aryloxy, aryl-thio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl)amino and (dihetaryl)amino, which comprises al) the reaction of an isonitrile complex of the general formula (II) R1-N.ident.C-M
(II) in which R1 and M have one of the aforementioned meanings, with a compound of the general formulae (III) or (IIIa) in which n, R2, R3, R4, R5, R6, R7 and R8 have one of the aforementioned meanings, X- is an anion equivalent, and Y is a leaving group.

9. The process according to claim 8 for preparing compounds of the general formula (I-A.2.1) where M, R1, R2, R3 and R7 have a meaning as defined in any of claims 1 to 7.

10. The process according to claim 8 or9, where R3, R4, R7, R8, and, if present, R5 and R6, are all hydrogen.

11. The process according to any of claims 1 to 7, for preparing compounds of the general formula (I-B.1) or (I-B.2) where M, R1, R2, R5, R6, R7 and R8 have a meaning as defined in any of claims 1 to 7, which comprises al) the reaction of an isonitrile complex of the general formula (II) R1-N.ident.C-M
(ll) in which R1 and M have one of the meanings given above, with a compound of the general formulae (lll-B.1), (lll-B.1.a), (lll-B.2) or (lll-B.2.a) in which R2, R5, R6, R7 and R8 have one of the meanings given above, X- is an anion equivalent, and Ya is unsubstituted or substituted alkyl, unsubstituted or substituted aryl or unsubstituted or substituted alkyl carbonyl.

12. The process according to claim 11 for preparing compounds of the general for-mula (I-B.2.1) where M, R1 and R2 have a meaning as defined in any of claims 1 to 7.

13. The process according to any of claims 1 to 7, for preparing compounds of the general formula (1-C.1) or (1-C.2) where M, R1, R2, R3a, R6, R7 and R8 have a meaning as defined in any of claims 1 to 7, which comprises al) the reaction of an isonitrile complex of the general formula (II) in which R1 and M have one of the meanings given above, with a compound of the general formulae (III-C.1) (III-C.1.a), (III-C.2) or (III-C.2.a) in which R2, R6, R7 and R8 have one of the meanings given above, X- is an anion equivalent, and ya is unsubstituted or substituted alkyl, unsubstituted or substituted aryl or unsubstituted or substituted alkyl carbonyl, and b1) subjecting the product obtained in step a1) to a further reaction with a com-pound R3a-Z, where Z is a leaving group, in the presence of a base.

14. The process according to claim 13 for preparing compounds of the general for-mula (I-C.2.1) where M, R1, R2 and R3a have a meaning as defined in any of claims 1 to 7.

15. The process according to claim 13 or 14, wherein R3a is selected from groups of the formulae V-A, V-B, V-C, V-D, V-E, V-F, V-G, V-H, V-I, V-K or V-L
wherein # represents the bonding site to the oxygen atom, T is selected from -O- and -NR Vf, wherein R Vf is hydrogen, alkyl, cycloalkyl or aryl, R Va, R Vb, and R Vh are selected from unsubstituted or substituted alkyl, unsubsti-tuted or substituted cycloalkyl, unsubstituted or substituted aryl and unsub-stituted or substituted hetaryl, R VC, R Vd, R Ve are independently of each other selected from unsubstituted or sub-stituted alkyl, unsubstituted or substituted cycloalkyl, unsubstituted or sub-stituted aryl and unsubstituted or substituted hetaryl, R Vg is selected from unsubstituted or substituted heterocycloalkyl, R Vi and R Vk are independently of each other selected from unsubstituted or sub-stituted alkyl, unsubstituted or substituted cycloalkyl, unsubstituted or sub-stituted aryl, alkoxy unsubstituted or substituted aryloxy and unsubstituted or substituted cycloalkyloxy, R Vm and R Vn, are independently of each other selected from unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or sub-stituted cycloalkyl, unsubstituted or substituted aryl and unsubstituted or substituted hetaryl, R Vo and R VP, are independently of each other selected from unsubstituted or sub-stituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substi-tuted cycloalkyl, unsubstituted or substituted aryl and unsubstituted or sub-stituted hetaryl, R Vt, R Vr and R Vs, are independently of each other selected from unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or sub-stituted cycloalkyl, unsubstituted or substituted aryl and unsubstituted or substituted hetaryl, R Vt, R Vu and R Vv, are independently of each other selected from unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or sub-stituted cycloalkyl, unsubstituted or substituted aryl and unsubstituted or substituted hetaryl, R Vw, R Vx and R Vy are independently of each other selected from unsubstituted or substituted alkyloxy, unsubstituted or substituted alkenyloxy, unsubstituted or substituted cycloalkyloxy and unsubstituted or substituted aryloxy, and D+ is a cation equivalent.

16. The process according to any of the preceding claims, in which the reaction in step al) is performed in the presence of a base, preferably selected from tertiary amines.

17. The process according to any of the preceding claims, in which the reaction in step b1) is performed in the presence of a base, preferably a non-nucleophilic base, in particular lithium bis(trimethylsilyl)amide.

18. The process according to any of claims 1 to 7, for preparing compounds of the general formula (I-E) where M, R1, R2, R3 and R8 have a meaning as defined in any of claims 1 to 7, which comprises a2) the reaction of an isonitrile complex of the general formula II

R1¨N.ident.C¨M (II) where R1 and M have one of the meanings given above, with a compound of the general formula (V) where R2, R3 and R8 have one of the meanings given above; and R10 and R11 are independently selected from C1-C4-alkyl or R10 and R11 to-gether are linear C2-C4-alkylene which may be substituted by one or more C1-C4 alkyl radicals;
to give an intermediate compound of the formula (VI) in which R1, R2, R3, R8, R10, R11 and M are as defined above, and b2) the treatment of the intermediate compound of the formula (VI) with an acid.

19. The process according to any of claims 1 to 7 for preparing compounds of the general formula (I-F) where R1, R2, R4, R7, R8, M and EWG are as defined above, which comprises a3) the reaction of an isonitrile complex of the general formula II
R1¨N.ident.C¨M (II) in which R1 and M are as defined above, with a compound of the general formulae (IIlb) or (IIlc) where X- is an anion equivalent; and R2, R4, R7, R8 and EWG are as defined above.

20. The process according to claim 18 or 19, where M is AuCl.

21. A compound of the general formula (l), as defined in any of claims 1 to 15, and 18 to 20.

22. A catalyst, comprising or consisting of a compound of the general formula (l), as defined in any of claims 1 to 15, and 18 to 20.

23. The use of a compound of the general formula (l), as defined in any of claims 1 to 15, and 18 to 20, as or in a catalyst employed in a C-C, C-O, C-N or C-H bond formation reaction.

24. The use according to claim 23 in a C-C coupling reaction, selected from the Su-zuki reaction, Heck reaction, Sonogashira reaction, Stille reaction and Kumada reaction.

25. The use according to claim 23 in a reaction, selected from the hydrogenation, hydroformylation, hydrosilylation, Hartwig-Buchwald reaction and amide .alpha.-arylation.

26. A compound of the general formula (Vl) where R1 is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl, R2 is selected from hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl and hetaryl, wherein R1 and R2 do not both stand for hydrogen;
R3 is hydrogen and in each case unsubstituted or substituted alkyl, alkoxy, al-kylthio, (monoalkyl)amino, (dialkyl)amino, cycloalkyl, cycloalkoxy, cycloal-kylthio, (monocycloalkyl)amino, (dicycloalkyl)amino, heterocycloalkyl, het-erocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl)amino, (dihet-erocycloalkyl)amino, aryl, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl)amino and (dihetaryl)amino;
R8 is hydrogen and in each case unsubstituted or substituted alkyl, alkoxy, al-kylthio, (monoalkyl)amino, (dialkyl)amino, cycloalkyl, cycloalkoxy, cycloal-kylthio, (monocycloalkyl)amino, (dicycloalkyl)amino, heterocycloalkyl, het-erocycloalkoxy, heterocycloalkylthio, (monoheterocycloalkyl)amino, (dihet-erocycloalkyl)amino, aryl, aryloxy, arylthio, (monoaryl)amino, (diaryl)amino, hetaryl, hetaryloxy, hetarylthio, (monohetaryl)amino and (dihetaryl)amino, wherein the two radicals R2 and R8 may also form together with the N atom to which R2 is bound a 3- to 12-membered, unsubstituted or substituted nitro-gen heterocycle which may optionally have 1, 2 or 3 further heteroatoms or heteroatom containing groups independently selected from O, N, NR a and S as ring members, wherein R a is hydrogen, alkyl, cycloalkyl or aryl R10 and R11 are independently selected from C1-C4-alkyl or R10 and R11 together are linear C2-C4-alkylene which may be substituted by one or more C1-C4 alkyl radicals; and M is a metal atom containing group.