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Transition metal complex containing asymmetric N-heterocyclic carbene structure as well as preparation method, catalyst system and application of transition metal complex

A nitrogen-heterocyclic carbene and transition metal technology, applied in the field of transition metal complexes, to achieve the effects of high yield, reduced production cost, and high purity

Pending Publication Date: 2022-03-22
常州汉韦聚合物有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The purpose of the present invention is to provide an asymmetric nitrogen-heterocyclic carbene structure in view of the current situation of the only vanadium complexes containing NHC ligands with symmetrical structures and the difficulty of directly preparing vanadium complexes containing NHC ligands with asymmetric structures. Transition metal complexes and preparation methods thereof do not need to use expensive strong bases (as potassium tert-butoxide) and air-sensitive NHC ligands, and use NHC hydrochlorides that are not sensitive to water and oxygen as raw materials. The silver compound can also be recycled to reduce production costs, and the target product yield and purity are high, which is of great significance to the wide application of the vanadium complex

Method used

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  • Transition metal complex containing asymmetric N-heterocyclic carbene structure as well as preparation method, catalyst system and application of transition metal complex
  • Transition metal complex containing asymmetric N-heterocyclic carbene structure as well as preparation method, catalyst system and application of transition metal complex
  • Transition metal complex containing asymmetric N-heterocyclic carbene structure as well as preparation method, catalyst system and application of transition metal complex

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preparation example Construction

[0028] A second aspect of the present invention provides a method for preparing a transition metal complex containing an asymmetric nitrogen heterocyclic carbene structure, comprising the following steps:

[0029] (1) reacting nitrogen-heterocyclic carbene hydrochloride and silver compound in the first organic solvent to obtain a silver complex containing nitrogen-containing heterocyclic carbene;

[0030] (2) reacting the silver complex of nitrogen-containing heterocyclic carbene obtained in step (1) with (V=O)XYZ in a second organic solvent to obtain the vanadium complex of nitrogen-containing heterocyclic carbene ligand.

[0031] According to the present invention, preferably, in step (1), the structure of the nitrogen-containing heterocyclic carbene hydrochloride is as shown in formula 1 or formula 2; the mole of silver in the nitrogen-containing heterocyclic carbene hydrochloride and the silver compound The ratio is 0.9:1~1.0:1, and the silver compound is Ag 2 O or AgCl, ...

Embodiment approach

[0033] According to a preferred embodiment of the present invention, the structure of the nitrogen-containing heterocyclic carbene hydrochloride is shown in Formula 1, and the silver compound is Ag 2 O, the reaction formula is as shown in formula 3:

[0034]

[0035]The preparation method of the present invention is efficient and convenient, does not use expensive strong base, that is, NHC hydrochloride which is not sensitive to water and oxygen is used as raw material, and Ag 2 O reaction to prepare the silver complex NHC AgCl containing NHC ligands, and further use the NHC AgCl complex as the NHC ligand transfer reagent to react with (V=O)XYZ to efficiently synthesize the vanadium complex NHC (V=O ) XYZ target product, and the yield is high, the purity is high, and the production cost is reduced.

[0036] According to the present invention, preferably, the first organic solvent and the second organic solvent are halogenated hydrocarbons; preferably, the first organic sol...

Embodiment 1

[0045] Add 1.565g of N-(2,4,6-trimethylphenyl)-N'-benzyl imidazole hydrochloride and silver oxide (the molar ratio of NHC to silver atoms in silver oxide is 1:1) into dichloromethane , reacted at 25° C. for 12 h under dark conditions, filtered the obtained solution, added hexane for recrystallization, and dried the recrystallized product to obtain 1.72 g of silver complex (NHC·AgCl), with a yield of 82%.

[0046] Add 0.42g of the above-synthesized silver complex and 0.17g of vanadium trichloride to dichloromethane, react at 20°C for 12 hours, filter to obtain the solution and AgCl, recrystallize the solution, and dry to obtain 0.36g of vanadium complex V1, the yield was 80%. The obtained AgCl can be used in the synthesis of the silver complex (NHC·AgCl) in the above steps, so as to realize the recycling of AgCl.

[0047] Compared with Comparative Example 1, the method adopted in Example 1 does not use potassium tert-butoxide as a strong base, does not need to separate the aza...

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Abstract

The invention belongs to the field of transition metal complexes, and relates to a transition metal complex containing an asymmetric N-heterocyclic carbene structure, a preparation method of the transition metal complex, a catalyst system and application of the complex and the catalyst system. The general formula of the transition metal complex containing the asymmetric N-heterocyclic carbene structure is NHC. (V = O) XYZ, NHC is an asymmetric N-heterocyclic carbene ligand, and X, Y and Z are the same or different and are independently selected from halogen and / or alkoxy; the preparation method of the complex comprises the following steps: reacting N-heterocyclic carbene hydrochloride with a silver compound to obtain the silver complex containing N-heterocyclic carbene; the obtained silver complex containing the nitrogen heterocyclic carbene reacts with (V = O) XYZ, and the vanadium complex containing the nitrogen heterocyclic carbene ligand is obtained. The transition metal complex containing the asymmetric N-heterocyclic carbene structure has potential application value in the aspects of asymmetric catalysis, product stereoselectivity regulation and control, biomedicine and the like.

Description

technical field [0001] The invention belongs to the field of transition metal complexes, and specifically relates to a transition metal complex containing an asymmetric nitrogen heterocyclic carbene structure, a preparation method thereof, a catalyst system, and applications of the complex and the catalyst system. Background technique [0002] Nitrogen heterocyclic carbene (NHC) is a kind of carbene that is relatively stable at room temperature. The electron-donating conjugation effect of the lone pair of electrons on the two nitrogen atoms connected to the carbene carbon atom to the empty orbital of the carbene carbon atom makes NHC have a strong Nucleophilicity, therefore, NHC has stronger electron donating ability and coordination ability than traditional phosphine ligands, and is widely used in the synthesis of metal complexes, see: Coordination Chemistry Reviews, 2020, 422:213334; ACS Catalysis, 2020 , 10:6862-6869. Among the many complexes containing NHC ligands, the v...

Claims

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Application Information

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IPC IPC(8): C07F1/10C07F9/00B01J31/22C08F210/06C08F210/16C08F4/68C08F32/00
CPCC07F1/00C07F9/00B01J31/2273C08F210/06C08F32/00B01J2231/70B01J2531/56C08F210/16C08F2500/01C08F2500/03C08F4/68
Inventor 张树吴一弦查慧刘相伟高正明林金汉
Owner 常州汉韦聚合物有限公司
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