CN108822152B - Osmium bidentate N-based complex with catalytic ammonia borane dehydrogenation activity and preparation method thereof - Google Patents
Osmium bidentate N-based complex with catalytic ammonia borane dehydrogenation activity and preparation method thereof Download PDFInfo
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- 229910052762 osmium Inorganic materials 0.000 title claims abstract description 32
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 title claims abstract description 32
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 title abstract description 10
- 230000000694 effects Effects 0.000 title abstract description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 12
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 150000005045 1,10-phenanthrolines Chemical class 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000001291 vacuum drying Methods 0.000 claims 1
- MYSMDZQWSJSWHW-UHFFFAOYSA-N azanylidyneosmium Chemical compound [Os]#N MYSMDZQWSJSWHW-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 239000012043 crude product Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 7
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 7
- 235000010703 Modiola caroliniana Nutrition 0.000 description 7
- 244000038561 Modiola caroliniana Species 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 4
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- GIEQBYJCGYHHSU-UHFFFAOYSA-N 4,7-dichloro-1,10-phenanthroline Chemical compound C1=CC2=C(Cl)C=CN=C2C2=C1C(Cl)=CC=N2 GIEQBYJCGYHHSU-UHFFFAOYSA-N 0.000 description 2
- JIVLDFFWTQYGSR-UHFFFAOYSA-N 4,7-dimethyl-[1,10]phenanthroline Chemical compound C1=CC2=C(C)C=CN=C2C2=C1C(C)=CC=N2 JIVLDFFWTQYGSR-UHFFFAOYSA-N 0.000 description 2
- NAZZKEZTSOOCSZ-UHFFFAOYSA-N 4-methyl-1,10-phenanthroline Chemical compound C1=CC2=CC=CN=C2C2=C1C(C)=CC=N2 NAZZKEZTSOOCSZ-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- WZMUUWMLOCZETI-UHFFFAOYSA-N azane;borane Chemical compound B.N WZMUUWMLOCZETI-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/002—Osmium compounds
- C07F15/0026—Osmium compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/825—Osmium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Materials Engineering (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an osmium bidentate N-based complex with catalytic ammonia borane dehydrogenation activity and a preparation method thereof, belonging to the technical field of inorganic synthesis and catalysis. Adding OsCl2(PPh3)3The osmium-nitrogen complex can be reacted with phenanthroline bidentate N-based active ligand in an organic solvent at room temperature to generate a series of osmium-nitrogen complexes. When the catalyst is applied to the catalytic ammonia borane dehydrogenation reaction, the catalyst has high catalytic reaction activity.
Description
Technical Field
The invention relates to an osmium bidentate N-based complex with catalytic ammonia borane dehydrogenation activity and a preparation method thereof, belonging to the technical field of inorganic synthesis and catalysis.
Background
In recent years, with the increasing energy and environmental problems, the development of sustainable clean energy systems to replace the existing energy carriers is urgent. The hydrogen energy becomes the first-choice novel energy source with a plurality of advantages of large reserve, wide distribution, high combustion value, zero pollution to the environment and the like. However, a safe and efficient hydrogen storage and transportation method is the key to the large-scale application of hydrogen energy. Chemical hydrogen storage has the advantages of high hydrogen storage density, good safety and the like, and has attracted wide attention in recent years. Wherein ammonia borane (NH)3BH3AB) a solid that is stable at room temperature by virtue of its theoretical hydrogen storage capacity of up to 19.6 wt% is the most potential chemical hydrogen storage material.
However, ammonia borane has various advantages as a potential hydrogen storage material, but still has the problems of high hydrogen release temperature in the hydrogen release process, impurity gas generation, volume expansion, difficult regeneration and the like in the hydrogen release process. For this reason, a series of studies for improving the hydrogen release performance of ammonia borane are rapidly spreading worldwide, such as supporting ammonia borane on porous materials, metal substitution chemical activation, using additives or catalysts, and the like. Among the many measures, the dehydrogenation of ammonia borane by metal catalysis is one of the most effective methods for improving the amount of hydrogen release, the selectivity and the kinetics of the hydrogen release reaction.
Currently, ammonia borane dehydrogenation catalysts that have been studied internationally involve a variety of metals in the early, intermediate and late transition series [ chem. rev.2010,110,4023-4078 ]. Among them, three transition metal catalysts of ruthenium, rhodium and iridium have exhibited relatively excellent performance [ Synthesis and Application of organic compounds. topics in organic chemical chemistry.2015,49, 153. 220 ], and their introduction has changed reaction path, reduced reaction activation energy, effectively increased hydrogen release reaction rate and reduced hydrogen release temperature. The third transition metal osmium, ruthenium, rhodium and iridium are in the VIII group of the periodic table of elements, and have certain similarity in properties, and the latter three are widely applied to the catalytic ammonia borane dehydrogenation reaction, so that the osmium metal has great possibility of being applied to the reaction and is expected to become a novel ammonia borane dehydrogenation catalyst.
Therefore, the development of new, highly efficient osmium catalysts with catalytic ammonia borane dehydrogenation activity is worthy of further exploration and development.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a novel osmium bidentate N-based complex catalyst with high efficiency for catalyzing ammonia borane dehydrogenation and a preparation method thereof.
The method for preparing the osmium bidentate N-base complex is characterized by comprising the following steps: adding OsCl2(PPh3)3Reacting with an active bidentate N-base ligand in an organic solvent to obtain the osmium bidentate N-base ligand.
The osmium bidentate diamine complex has the following structure:
further, in the above technical scheme, the bidentate N ligand is selected from 1, 10-phenanthroline or substituted 1, 10-phenanthroline.
Preferably, the first and second electrodes are formed of a metal,
further, in the above technical scheme, the reaction is carried out under anhydrous and oxygen-free conditions.
Further, in the above technical solution, the OsCl2(PPh3)3The molar ratio to the active bidentate N ligand is 1:1-2, preferably 1:1.2, and the reaction temperature is between 20 and 25 ℃.
Further, in the above technical solution, the reaction solvent is selected from dichloromethane, chloroform, tetrahydrofuran or 1, 2-dichloroethane. Dichloromethane solvents are preferred.
The specific reaction steps comprise:
(1) preparation of crude osmium bidentate N-base complex: adding OsCl into a reaction bottle2(PPh3)3Adding an anhydrous solvent to dissolve the bidentate N-based ligand, stirring the mixture to react, and concentrating the mixture under reduced pressure to obtain a crude product of the osmium bidentate N-based ligand complex;
(2) purification of crude osmium bidentate N-base complex: washing the crude product by using an anhydrous solvent, filtering and drying to obtain a purified osmium bidentate N-based complex solid;
OsCl in step (1)2(PPh3)3The molar ratio of the N-base ligand to the bidentate N-base ligand is 1:1-2, and the reaction condition is that the mixture is stirred for 1-10h at the temperature of 15-30 ℃. The preferable reaction condition is that the mixture is stirred for 4 hours at the temperature of 20-25 ℃;
the organic solvent washing solvent in the step (2) is selected from n-pentane, n-hexane or n-heptane. The preferred solvent is n-hexane, and the number of washing times is preferably 4.
Preferably, the drying in the step (2) is carried out by adopting vacuum/high-purity nitrogen flow switching, and the switching frequency is 0.5-1 h/time;
in the present invention, the high-purity nitrogen gas used in the drying is a nitrogen gas having a purity of 99.95% to 99.99%.
The invention has the beneficial effects that:
the preparation method of the osmium bidentate N-based complex has the advantages of simple steps, mild reaction conditions and low energy consumption, and is suitable for large-scale production. The obtained complex shows excellent catalytic activity in catalyzing ammonia borane dehydrogenation reaction.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Weighing 1, 10-phenanthroline (45mg,0.25mmol) and OsCl2(PPh3)3(220mg,0.21mmol) was charged into a 25mL magneton reaction flask under N2Under protection, 15mL of dichloromethane solvent is added, the mixture is stirred and reacts for 4 hours at the temperature of 20-25 ℃, and the solution is changed into purple black from dark green. After the reaction is finished, concentrating the reaction solution, and adding 20mL of anhydrous n-hexane to form a mauve precipitate, namely the 1, 10-phenanthroline substituted osmium nitrogen complex crude product. And washing the crude product by using normal hexane (4 times, 40mL), filtering and drying to obtain the purified osmium nitrogen complex mauve solid with the yield of 148mg and 73%.
The result of the nuclear magnetic resonance analysis was1H NMR(400MHz,CDCl3):8.9(s,2H,Ar),7.9(d,J＝8.0Hz,2H,Ar),7.8(s,2H,Ar),7.0(d,J＝5.6Hz,2H,Ar),7.3(t,J＝7.2Hz,12H,PPh3),7.1(t,J＝7.0Hz,6H,PPh3),6.9(t,J＝7.2Hz,12H,PPh3).13C{1H}NMR(101MHz,DMSO)}:157.0(s,Ar),150.1(s,Ar),136.2(s,Ar),135.7(s,PPh3),130.3(s,Ar),129.4(s,PPh3),127.8(s,Ar),127.3(broad s,PPh3),124.6(s,Ar).31P{1H}NMR(162MHz,CDCl3)}:-16.2(s,PPh3).
Elemental analysis (%) theoretical value (OsC)48H38N2P2Cl2) C, 59.69; h, 3.97; n,2.90. found: c, 70.48; h, 4.11; and N,2.88.
Example 2
Weighing 4-methyl-1, 10-phenanthroline (49mg,0.25mmol) and OsCl2(PPh3)3(220mg,0.21mmol) was charged into a 25mL magneton reaction flask under N2Under protection, adding 15mL of dichloromethane solvent, stirring and reacting for 4 hours at 20-25 ℃, and changing the color of the solution from dark greenBecoming purple black. After the reaction is finished, concentrating the reaction solution, and adding 20mL of anhydrous n-hexane to form a mauve precipitate, namely the crude product of the 4-methyl-1, 10-phenanthroline substituted osmium nitrogen complex. And washing the crude product by using normal hexane (4 times, 40mL), filtering and drying to obtain the purified osmium nitrogen complex mauve solid with the yield of 158mg and 77%.
The result of the nuclear magnetic resonance analysis was1H NMR(600MHz,CDCl3)δ:8.9(d,J＝7.8Hz,1H,Ar),8.8(d,J＝8.4Hz,1H,Ar,),8.0(d,J＝13.2Hz,1H,Ar),7.9(d,J＝12.0Hz,1H,Ar),7.8(d,J＝13.8Hz,1H,Ar),7.3(d,J＝10.2Hz,12H,PPh3),7.1(t,J＝10.8Hz,6H,PPh3),7.0(t,J＝10.5Hz,13H,PPh3and Ar),6.9(d,J＝7.8Hz,1H,Ar),2.8(s,3H,CH3).13C{1H}NMR(151MHz,CDCl3)δ:156.2(s,Ar),155.3(s,Ar),150.0(s,Ar),149.4(s,Ar),143.1(s,Ar),134.9(broad s,PPh3),133.1(s,Ar),131.1(s,Ar),128.7(s,Ar),127.6(s,PPh3),125.9(d,J＝2.2Hz,,PPh3),125.6(s,Ar),123.7(s,Ar),122.6(s,Ar),122.4(s,Ar),17.3(s,CH3).31P{1H}NMR(243MHz,CDCl3)δ:-14.5(s,PPh3).
Elemental analysis (%) theoretical value (OsC)49H40N2P2Cl2) C, 60.06; h, 4.11; n,2.86, found: c, 60.11; h, 4.08; n,2.78.
Example 3
Weighing 4, 7-dimethyl-1, 10-phenanthroline (52mg,0.25mmol) and OsCl2(PPh3)3(220mg,0.21mmol) was charged into a 25mL magneton reaction flask under N2Under protection, 15mL of dichloromethane solvent is added, the mixture is stirred and reacts for 4 hours at the temperature of 20-25 ℃, and the solution is changed into purple black from dark green. After the reaction is finished, concentrating the reaction solution, and adding 20mL of anhydrous n-hexane to form a mauve precipitate, namely the crude product of the 4, 7-dimethyl-1, 10-phenanthroline substituted osmium nitrogen complex. And washing the crude product by using normal hexane (4 times, 40mL), filtering and drying to obtain the purified osmium nitrogen complex mauve solid with the yield of 148mg and the yield of 71%.
Nuclear magnetic resonance analysis resultsIs composed of1H NMR(600MHz,CD2Cl2)δ:8.8(s,2H,Ar),8.0(s,2H,Ar),7.3(d,J＝6.0Hz,12H,PPh3),7.1(t,J＝6.6Hz,6H,PPh3),7.0(t,J＝6.6Hz,12H,PPh3),6.9(broad s,2H,Ar),2.8(s,6H,CH3).13C{1H}NMR(151MHz,CD2Cl2)δ:156.4(s,Ar),150.2(s,Ar),144.5(s,Ar),136.0(s,PPh3),129.7(s,Ar),128.6(s,PPh3),126.7(broad s,PPh3),124.6(s,Ar),123.3(s,Ar),18.4(s,CH3).31P{1H}NMR(243MHz,CD2Cl2)δ:-14.5(s,PPh3).
Elemental analysis (%) theoretical value (OsC)50H42N2P2Cl2) C, 60.42; h, 4.26; n,2.82. found: c, 60.55; h, 4.16; and N,2.66.
Example 4
Weighing 4, 7-dichloro-1, 10-phenanthroline (63mg,0.25mmol) and OsCl2(PPh3)3(220mg,0.21mmol) was charged into a 25mL magneton reaction flask under N2Under protection, 15mL of dichloromethane solvent is added, the mixture is stirred and reacts for 4 hours at the temperature of 20-25 ℃, and the solution is changed from dark green to blue-purple. After the reaction is finished, concentrating the reaction solution, and adding 20mL of anhydrous n-hexane to form a bluish purple precipitate, namely the crude product of the 4, 7-dichloro-1, 10-phenanthroline substituted osmium nitrogen complex. And washing the crude product by using normal hexane (4 times, 40mL), filtering and drying to obtain the purified osmium nitrogen complex mauve solid with the yield of 150mg and the yield of 69%.
The result of the nuclear magnetic resonance analysis was1H NMR(400MHz,CDCl3)δ:8.9(d,J＝6.1Hz,2H,Ar),8.3(s,2H,Ar),7.3(broad s,12H,PPh3),7.2(t,J＝6.8Hz,6H,PPh3),7.1(d,J＝6.1Hz,2H,Ar),7.0(t,J＝6Hz,12H,PPh3).13C{1H}NMR(151MHz,CDCl3)δ:156.8(s,Ar),151.7(s,Ar),141.0(s,Ar),135.9(s,PPh3),129.0(s,PPh3),128.7(s,Ar),127.1(broad s,PPh3),124.5(s,Ar),124.2(s,Ar).31P{1H}NMR(243MHz,CDCl3)δ:-17.8(s,PPh3).
Elemental analysis (%) theoretical value (OsC)52H46N2P2Cl2) C, 61.11; h, 4.54; n,2.74, found: c, 61.38; h, 4.75; and N,2.66.
Example 5
Test for catalytic Performance
Using the osmium bidentate N-based complex prepared in examples 1-4 as a catalyst, a dry 25mL Schlenk flask was charged with ammonia borane (1.77mmol) in tetrahydrofuran (5mL) and osmium bidentate N-based complex catalyst (0.09mmol) in ethylene glycol dimethyl ether (8mL) under anhydrous and oxygen-free conditions, and the side ports of the Schlenk flask were closed after mixing. The side branch was then connected to a plastic tube attached to a burette for measuring gas, and the Schlenk bottle was transferred to a 60 ℃ oil bath, the magneton speed was controlled at 300rpm, the branch and stopwatch were opened, hydrogen gas was collected and the time was recorded. The volume of hydrogen was recorded at different time intervals.
The results of the experiments that the osmium N-based complex catalysts prepared in examples 1 to 4 catalyze the ammonia borane to release hydrogen when the catalyst loading is 5 mol% in the tetrahydrofuran/ethylene glycol dimethyl ether mixed solution (volume ratio is 1:1.6) at 60 ℃ are shown in Table 1, and it can be seen from the results of the experiments that the synthesized osmium N-based complex as a catalyst has good catalytic activity and can release 2.12 to 2.29 equivalents of H from the ammonia borane2. The osmium N-based complex has potential application as a high-efficiency osmium catalyst for ammonia borane dehydrogenation.
aCalculated according to the time required for the release of 1 equivalent of oxygen.
Table 1 examples 1-4 preparation of osmium N-based complexes to catalyze the dehydrogenation of ammonia boranes
The foregoing embodiments have described the general principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, and that various changes and modifications may be made without departing from the scope of the principles of the present invention, and the invention is intended to be covered by the appended claims.
Claims (8)
1. An osmium bidentate N-based complex catalyst is characterized by having the following chemical structure:
2. the process for preparing an osmium bidentate N-base complex according to claim 1, comprising the following operations: OsCl2(PPh3)3And reacting with a bidentate N-base ligand in a solvent to obtain the complex.
3. The process for preparing an osmium bidentate N-base complex according to claim 2, wherein: the bidentate N-base ligand is selected from 1, 10-phenanthroline or substituted 1, 10-phenanthroline.
4. The process for preparing an osmium bidentate N-base complex according to claim 2, wherein: the reaction solvent is selected from dichloromethane, chloroform, tetrahydrofuran or 1, 2-dichloroethane.
5. The process for preparing an osmium bidentate N-base complex according to claim 2, wherein: the reaction is carried out under the anhydrous and oxygen-free conditions, and the reaction temperature is 20-25 ℃.
6. The process for preparing an osmium bidentate N-base complex according to claim 2, wherein: the OsCl2(PPh3)3The molar ratio to bidentate N-based ligand is 1: 1-2.
7. A process for the preparation of an osmium bidentate N-based complex according to any of claims 2 to 6, wherein: the complex is washed by anhydrous solvent and purified after vacuum drying; the washing solvent is selected from n-pentane, n-hexane or n-heptane.
8. The use of the osmium bidentate N-base complex according to claim 1 to catalyze the dehydrogenation of ammonia borane, wherein: the osmium bidentate N-based complex is used to catalyze ammonia borane dehydrogenation reactions.
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