CN117263961A - Cu with hardness and softness combined 3 Cluster catalytic material and application thereof in three-component dehydrogenation coupling reaction - Google Patents
Cu with hardness and softness combined 3 Cluster catalytic material and application thereof in three-component dehydrogenation coupling reaction Download PDFInfo
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- 238000005859 coupling reaction Methods 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 19
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 title abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 57
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000003446 ligand Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 2
- 230000002093 peripheral effect Effects 0.000 claims description 2
- 125000006514 pyridin-2-ylmethyl group Chemical group [H]C1=C([H])C([H])=C([H])C(=N1)C([H])([H])* 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 229910052802 copper Inorganic materials 0.000 abstract description 20
- 239000000758 substrate Substances 0.000 abstract description 9
- -1 pyridine-2-ylmethyl Chemical group 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 150000001345 alkine derivatives Chemical class 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 6
- UWYZHKAOTLEWKK-UHFFFAOYSA-N 1,2,3,4-tetrahydroisoquinoline Chemical compound C1=CC=C2CNCCC2=C1 UWYZHKAOTLEWKK-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000002447 crystallographic data Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000010813 internal standard method Methods 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
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- 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
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
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- C07C227/10—Formation of amino groups in compounds containing carboxyl groups with simultaneously increasing the number of carbon atoms in the carbon skeleton
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- C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
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- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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Abstract
The invention discloses a Cu with both hardness and softness 3 A cluster catalytic material and application thereof in three-component dehydrogenation coupling reaction belong to the crossing field of coordination chemistry and nano materials. The copper cluster enantiomer is synthesized by using 4, 5-diphenyl-1, 3-bis (pyridine-2-ylmethyl) -4, 5-dihydro-1H-imidazole-3-ammonium chloride as a protective ligand through a simple one-pot method, and has high yield. The chemical formula of the cluster is: c (C) 91 H 87 Cu 3 F 18 N 17 P 3 Abbreviated as: cu (Cu) 3 NC (NHC) Belongs to a triclinic system, and the space group isP‑1，a=14.8470(1)Å，b=16.7001(2)Å，c=19.3691(2)Å，α=91.311(1)°，β=94.283(1)°，γ=96.504(1)°，V=4755.88(8)Å 3 . The catalyst utilizes the advantages of hardness and softness and realizes high-efficiency catalysis multifunctional three-component dehydrogenation coupling reaction, including excellent regioselectivity (reaching 100%), high efficiency (conversion number (TON) =3800 and 1840), high yield (reaching 99%), wide substrate range (85) and mild conditions (room temperature), and development of the functionalized cluster catalyst is realized.
Description
Technical Field
The invention belongs to the crossing field of coordination chemistry and nano materials, and mainly synthesizes novel Cu modified by carbene 3 The cluster catalyst material is highly effective in multifunctional catalysis of three-component dehydrogenation coupling reaction.
Background
The preparation and research of atomic accurate metal nanoclusters has become a brand-new and promising research direction in the field of nanoscience. Metal nanoclusters are a class of cluster compounds having an accurate atomic structure composed of ten to several hundred metal atoms bridged by organic ligands. The metal nanoclusters are used as bridges for connecting atoms and nanoparticles, and exhibit unique optical, electrical and chemical properties. Compared with gold and silver, copper has the advantages of low price, high crust abundance, wide sources and the like. However, the synthesis of highly active copper cluster catalysts remains a great challenge due to the difficulty of copper cluster synthesis and the ease of oxidation in air, and research into copper clusters remains in the initiation phase, particularly for the atomic precision carbene-modified copper cluster catalysts.
The three-component dehydrogenation coupling reaction of alkyne is an important organic chemical reaction, a novel C-C, C-N bond is directly constructed through the three-component dehydrogenation coupling reaction, the controllable and diverse functionalization of alkyne is realized, the functionalized organic heterocyclic molecular compound is prepared, the utilization rate of atoms is greatly improved, the atomic economy advocated by the chemical research at present is met, in particular to the research fields of pharmacy and other fine chemicals, the propargylamine product is an important organic intermediate for organic synthesis, drug synthesis and industrial compound synthesis with high added value, and therefore, a great deal of research is carried out on the synthesis of propargylamine compounds.
Copper catalysts are one of the most representative catalysts for catalyzing the three-component dehydrogenation coupling reaction of alkynes. However, the research on copper-catalyzed alkyne three-component dehydrogenation coupling reaction still faces the following challenges: 1. under mild conditions, lack of ability to catalyze A with high efficiency and high regioselectivity 3 Coupling reaction and redox-A 3 Catalytic systems for reactions (a broad range of substrates including aliphatic aldehydes, alkynes and amines). 2. A new type of copper-based catalyst that is efficient and practical to achieve both reactions at room temperature is highly desirable.
Disclosure of Invention
The invention aims to synthesize Cu with high-efficiency and multifunctional carbene ligand protection 3 Cluster catalysts, and develop a highly efficient, multifunctional and practical method for preparing important organic intermediates propargylamine-based compounds.
Therefore, the invention develops a carbene modified small-core Cu 3 A clustered material characterized by: the chemical formula is as follows: c (C) 91 H 87 Cu 3 F 18 N 17 P 3 Abbreviated as: cu (Cu) 3 NC (NHC) Belongs to a triclinic system, the space group is P-1, α＝91.311(1)°，β＝94.283(1)°，γ＝96.504(1)°，
the shell ligand used is 4, 5-diphenyl-1, 3-bis (pyridin-2-ylmethyl) -4, 5-dihydro-1H-imidazole-3-ammonium chloride, and the structural formula is as follows:
Cu 3 NC (NHC) the shell of the cluster protects the ligand (NHC).
Cu of the invention 3 The preparation method of the cluster material is realized by the following steps:
combining a carbene ligand with an excess of KPF 6 Dissolving in water, stirring at room temperature, centrifuging the upper liquid after the reaction is finished, and collecting a solid product; the solid compound was dissolved in acetonitrile liquid and transferred to a flask, then Cu powder was added under stirring at room temperature, and the reaction was stirred at room temperature. After stopping the reaction, filtering with diatomite to remove Cu powder, adding an unfavorable solvent into the clear solution, volatilizing at room temperature to culture single crystals, filtering the obtained crystals, washing with diethyl ether, and drying in vacuum.
The copper nanocluster has a core composed of three copper atoms, and is protected and stabilized by three carbene ligands (shown in figure 1) 3 Metal core, peripheral three PFs 6 - The anions balance the cluster charge; three copper atoms are arranged in a triangle, three carbene ligands and Cu 3 The planes of the cores are vertically distributed, and each carbene ligand is coordinated with Cu in the same way through Cu-C bond and Cu-N bond 3 Kernel bonding (shown in fig. 2).
The carbene modified copper cluster catalyst can be used for efficiently and multifunctional catalyzing alkyne three-component dehydrogenation coupling reaction, and the properties of the carbene modified copper cluster catalyst are specifically described as follows:
the clusterThe material catalyst fully utilizes the advantages of hardness and softness in the three-component dehydrogenation coupling reaction, and realizes the high-efficiency catalytic multifunctional three-component dehydrogenation coupling reaction (A) 3 Coupling reaction and redox-A 3 Coupling reactions), including excellent regioselectivity (up to 100%), high efficiency (conversion (TON) =3800 and 1840), high yield (up to 99%), broad substrate range (85 examples, including various aliphatic and aromatic alkynes, various aliphatic and aromatic aldehyde compounds and various aliphatic and aromatic secondary amine substrates) (shown in fig. 3 and 4), mild conditions (room temperature) and high stability (a 3 The coupling reaction is cycled and catalyzed 5 times and redox-A 3 The coupling reaction is circularly catalyzed for 3 times), the amplification experiment is successfully carried out (the yield is more than 95 percent) (shown in figure 5) and is used for efficiently catalyzing the synthesis of biomolecules containing large substituents (shown in figure 6), so that the development of the functionalized cluster catalyst is realized.
The invention has the beneficial effects that: cu of the invention 3 The clusters have structures with accurate atomic sizes, and the structures can be accurately characterized on an atomic level; the carbene ligand endows rigidity and flexibility with dual properties, realizes efficient and multifunctional catalysis alkyne three-component dehydrogenation coupling reaction under mild conditions, has strong substrate universality, has very good application value for preparing propargylamine organic intermediate compounds, can efficiently catalyze synthesis of biomolecules containing large substituent groups, and has good application prospect in the field of organic catalysis.
Drawings
FIG. 1 is a Cu of the present invention 3 Schematic diagram of shell protection ligand structure of copper cluster material.
FIG. 2 is a Cu of the present invention 3 Schematic structural diagram of copper cluster material.
FIG. 3 is a Cu of the present invention 3 Copper cluster material catalysis A 3 Coupling reaction substrates.
FIG. 4 is a Cu of the present invention 3 Copper cluster material catalyzed redox-A 3 Coupling reaction substrates.
FIG. 5 is a Cu of the present invention 3 Copper cluster material catalysis A 3 Coupling reaction and redox-A 3 Amplification experiments of the coupling reactions.
FIG. 6 is a Cu of the present invention 3 The copper cluster material is used for preparing bioactive macromolecules in a catalytic mode.
Detailed Description
The invention is further illustrated by the following examples:
example 1: cu of the invention 3 Synthesis of copper cluster materials
Carbene ligand (1.0 mmol) and KPF 6 (2.2 mmol) in 40ml water, stirring at room temperature, centrifuging the upper liquid after the reaction is finished, and collecting white solid product; the white solid compound was dissolved in acetonitrile liquid (30 ml) and transferred to a flask, and then Cu powder (5 mmol) was added under stirring at room temperature, and stirred at room temperature for one day. After stopping the reaction, filtering with diatomite to remove Cu powder, adding an unfavorable solvent into the clear solution, volatilizing and culturing single crystals at room temperature to obtain crystals, filtering, washing with diethyl ether, and vacuum drying.
The Cu of the present invention obtained in example 1 was taken 3 The copper cluster material is further characterized, and the process is as follows:
(1) Crystal structure determination
The X-ray single crystal diffraction data of the complex was measured on a Rigaku XtaLAB Pro single crystal diffractometer using a single crystal sample of appropriate size. The data are all obtained by using CuK alpha rays which are monochromized by graphiteThe diffraction sources were collected by ω scan at 200K temperature and were subjected to Lp factor correction and semi-empirical absorption correction. The structural analysis is that the initial structure is obtained by a direct method through the SHELXS-97 program, and then the SHELXL-97 program is used for finishing by a full matrix least square method. All non-hydrogen atoms were refined using anisotropic thermal parameters. All hydrogen atoms were refined using isotropic thermal parametric methods. The detailed crystal measurement data are shown in Table 1.
TABLE 1 principal crystallographic data of the nano-copper cluster material of the invention
TABLE 1 primary crystallographic data
R 1 ＝∑||F o |-|F c ||/∑|F o |.wR 2 ＝[∑w(F o 2 -F c 2 ) 2 /∑w(F o 2 ) 2 ] 1/2
Application example 1: cu (Cu) 3 Copper cluster catalyst A 3 The coupling reaction uses 9-acetylene phenanthrene, benzaldehyde and dibenzylamine as reaction substrates.
At N 2 2.5mol% of Cu according to the invention in an atmosphere 3 The copper cluster catalyst, 600mg of activated molecular sieve and 1.5mL of anhydrous dichloromethane are sequentially added into a 10mL dry Schlenk reaction flask, and stirred for 5mins at room temperature; 0.2mmol of benzaldehyde and 0.2mmol of 9-acetylenephenanthrene are sequentially added to the stirred reaction solution, and the reaction is stirred for 5mins at room temperature; 0.3mmol of dibenzylamine and 0.5mL of anhydrous methylene chloride were added successively to the stirred reaction solution, and the reaction was stirred at room temperature for 12 hours. The complete reaction of reactants 9-acetylene phenanthrene and benzaldehyde is confirmed by TLC (thin layer chromatography) plate analysis, then the reaction is quenched, 0.2mmol of mesitylene is added as an internal standard, the catalytic yield is determined by a nuclear magnetic internal standard method, three experiments are performed in parallel, and an average value is taken to calculate the catalytic yield; finally, the crude product was concentrated and purified by column chromatography to give the target molecule propargylamine compound in 95% yield (fig. 3,4 ay).
Application example 2: cu (Cu) 3 Copper cluster catalyst for catalyzing redox-A 3 The coupling reaction uses phenylacetylene, benzaldehyde and 1,2,3, 4-tetrahydroisoquinoline as reaction substrates.
At N 2 0.25mol% of Cu according to the invention in an atmosphere 3 The copper cluster catalyst, 600mg of activated molecular sieve and 1.5mL of anhydrous dichloromethane are sequentially added into a 10mL dry Schlenk reaction flask, and stirred for 5mins at room temperature; 0.2mmol of benzaldehyde and 0.2mmol of phenylacetylene were successively added to the stirred reaction solutionThe reaction was stirred at room temperature for 5mins;0.3mmol of 1,2,3, 4-tetrahydroisoquinoline and 0.5mL of anhydrous dichloromethane were sequentially added to the stirred reaction solution, and the reaction was stirred at room temperature for 40h. The complete reaction of reactants phenylacetylene and benzaldehyde is confirmed by TLC (thin layer chromatography) plate analysis, then the reaction is quenched, 0.2mmol of mesitylene is added as an internal standard, the catalytic yield is determined by a nuclear magnetic internal standard method, three experiments are performed in parallel, and an average value is taken to calculate the catalytic yield; finally, the crude product was concentrated and purified by column chromatography to give a single target molecule of the C1-propargylamine class with a yield of 98% and a regioselectivity of 100% (FIGS. 4,5 a).
The above examples are only for illustrating the contents of the present invention, and other embodiments of the present invention are also provided. However, all technical solutions formed by adopting equivalent substitution or equivalent deformation are within the protection scope of the present invention.
Claims (3)
1. Cu modified by carbene 3 A clustered material characterized by: the chemical formula is as follows: c (C) 91 H 87 Cu 3 F 18 N 17 P 3 Abbreviated as: cu (Cu) 3 NC (NHC) Belongs to a triclinic system, the space group is P-1, α＝91.311(1)°，β＝94.283(1)°，γ＝96.504(1)°，/>
the shell ligand used is 4, 5-diphenyl-1, 3-bis (pyridin-2-ylmethyl) -4, 5-dihydro-1H-imidazole-3-ammonium chloride, and the structural formula is as follows:
Cu 3 NC (NHC) the shell of the cluster protects the ligand NHC.
2. The carbene-modified Cu of claim 1 3 A clustered material characterized by: the core consists of three copper atoms, and three carbene ligands are used for protecting and stabilizing Cu 3 Metal core, peripheral three PFs 6 - The anions balance the cluster charge; three copper atoms are arranged in a triangle, three carbene ligands and Cu 3 The planes of the cores are vertically distributed, and each carbene ligand is coordinated with Cu in the same way through Cu-C bond and Cu-N bond 3 Kernel bonding.
3. A carbene-modified Cu according to claim 1 or 2 3 The application of the cluster material in catalyzing the dehydrogenation coupling reaction of three components is characterized in that: as catalyst for A 3 Coupling reaction and redox-A 3 And (3) coupling reaction.
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