Asymmetric bis-(N-heterocyclic carbene) nickel (II) dihalide and preparation thereof

A nitrogen-heterocyclic carbene and dihalide technology, applied in the field of asymmetric bis-nickel dihalides, can solve the problems of unseen, unseen substituents, differences, etc., and achieve short reaction time, easy purification of products, and high reaction temperature low effect

Inactive Publication Date: 2009-07-22
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0012] However, so far there is no information on passing (1-H-Ind) 2 The step-by-step reaction of Ni with different imidazolium salts to synthesize asymmetric nickel(II) heterocyclic carbene complexes with different carbene ligands has been reported, and no such asymmetric nickel(II) double Related reports on the different substituents on the two nitrogen atoms of a nitrogen heterocyclic carbene ligand in nitrogen heterocyclic carbene complexes

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] Example 1: {[(R 1 NCHCHNR 1 )C]Ni[(R 3 NCHCHNR 5 )C]X 2 ; Substituent R on the 1,3 position of azacyclic carbene 1 , R 3 and R 5 Synthesis of isopropyl, 2,6-diisopropylphenyl and benzyl} respectively (taking X=Cl as an example)

[0042] will [(R 1 NCHCHNR 1 )CH]Cl (0.38 g, 2.0 mmol) in dichloromethane was added to (1-H-Ind) 2 Ni (0.58 g, 2.0 mmol) in tetrahydrofuran solution, stirred and reacted at 45 °C overnight, removed the solvent, washed with hexane, dried by suction, extracted with toluene, centrifuged the clear liquid, concentrated, frozen at -10 °C, and precipitated ( 1-H-Ind)Ni[(R 1 NCHCHNR 1 )C]Cl as black-red crystals (73%).

[0043] will [(R 3 NCHCHNR 5 )CH]Cl (0.71 g, 2.0 mmol) in toluene was added to (1-H-Ind)Ni[(R 1 NCHCHNR 1 )C]Cl (0.72 g, 2.0 mmol) in toluene solution, refluxed overnight, cooled and removed the solvent, extracted with toluene, centrifuged the supernatant, added a small amount of hexane, concentrated, frozen at 0 °C, and ...

Embodiment 2

[0044] Example 2: {[(R 1 NCHCHNR 1 )C]Ni[(R 3 NCHCHNR 5 )C]X 2 ; Substituent R on the 1,3 position of azacyclic carbene 1 , R 3 and R 5 Synthesis of mesityl, isopropyl and benzyl} respectively (taking X=Br as an example)

[0045] will [(R 1 NCHCHNR 1 )CH]Br (0.77 g, 2.0 mmol) in dichloromethane was added to (1-H-Ind) 2 Ni (0.58 g, 2.0 mmol) in tetrahydrofuran solution, stirred and reacted at 45 °C overnight, removed the solvent, washed with hexane, dried by suction, extracted with toluene, centrifuged the clear liquid, concentrated, frozen at -10 °C, and precipitated ( 1-H-Ind)Ni[(R 1 NCHCHNR 1 )C]Br as black-red crystals (70%).

[0046] will [(R 3 NCHCHNR 5 )CH]Br (0.56 g, 2.0 mmol) in toluene was added to (1-H-Ind)Ni[(R 1 NCHCHNR 1 )C]Br (1.12 g, 2.0 mmol) in toluene solution, refluxed overnight, cooled and removed the solvent, extracted with toluene, centrifuged the clear liquid, added a small amount of hexane, concentrated, frozen at 0 °C, and a large amoun...

Embodiment 3

[0047] Example 3: {[(R 1 NCR 2 CR 2 NR 1 )C]Ni[(R 3 NCR 4 CR 4 NR 5 )C]X 2 ;R 1 , R 2 , R 4 is methyl; R 3 and R 5 The synthesis of mesityl and benzyl} respectively (taking X=Br as an example)

[0048] will [(R 1 NCR 2 CR 2 NR 1 )CH]Cl (2.0 mmol) in dichloromethane was added to (1-CH 3 -Ind) 2 Ni (2.0 mmol) in benzene solution, stirred and reacted at 45°C overnight, removed the solvent, washed with n-heptane, dried by suction, extracted with toluene, centrifuged the clear liquid, concentrated, frozen at -10°C, and precipitated (1- CH 3 -Ind)Ni[(R 1 NCR 2 CR 2 NR 1 )C]Br as black-red crystals (76%).

[0049] will [(R 3 NCR 4 CR 4 NR 5 )CH]Br (2.0 mmol) in toluene was added to (1-CH 3 -Ind)Ni[(R 1 NCR 2 CR 2 NR 1 )C]Br (2.0 mmol) in ethyl acetate solution, refluxed overnight, cooled and removed the solvent, extracted with toluene, centrifuged the supernatant, added a small amount of hexane, concentrated, and frozen at 0 °C, a large amount of [ (...

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Abstract

The invention discloses an asymmetric bis-(N-heterocyclic carbene) nickel (II) dihalidee Ni (NHC) (NHC) X2 and a preparation method thereof. At normal pressure, the asymmetric dual-(N-heterocyclic carbene) nickel (II) dihalidee is synthesized through the double decomposition-elimination reaction between bisindenyl nickel and azole salt. The reaction condition of the method is mild, the reaction temperature is lower than that of the prior art and the reaction time is shorter. Additionally, the method is easy to operate and the product is easy to refine; more important, the method has controllability; with the controllability, an asymmetric bis-(N-heterocyclic carbene) nickel (II) dihalidee containing two different NHC ligands can be optionally synthesized through controlling reaction sequence and reaction temperature; and furthermore, the substituent of the two nitrogen atoms on one of the ligands are different and the method has wide applicable scope.

Description

technical field [0001] The invention relates to an asymmetric bis-(azacyclic carbene) nickel (II) dihalide and a method thereof, in particular to a method prepared by a normal pressure metathesis-elimination reaction between bisindenyl nickel (II) and an imidazole salt A method for asymmetric bis-(azacyclocarbene)nickel(II) dihalides. Background technique [0002] Since the first room-temperature stable nitrogen heterocyclic carbene (NHC) was isolated by Arduengo in 1991, this type of carbene has the characteristics of low toxicity, easy synthesis, easy regulation of steric hindrance and electronic effects, and strong σ-electron donating ability. It has been widely used in the design and synthesis of late transition metal catalysts as an alternative to traditional organic phosphines (see: ① Arduengo, III A.J.; Harlow, R.L.; Kline, M.J.Am.Chem.Soc. D.; Guerret, O.; Gabbai, F.P.; Bertrand, G. Chem. Rev. 2000, 100, 39; ③ Herrmann, W. A. ​​Angew. Chem. Int. Ed. 2002, 41, 1290)....

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/04C07B53/00B01J31/22
Inventor 孙宏枚谢玲芝刘志宏沈琪
Owner SUZHOU UNIV
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