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Method for synthesizing metal N-heterocyclic carbene complex

A technology for nitrogen heterocyclic carbene and heterocyclic carbene, which is applied in the field of synthesizing metal nitrogen heterocyclic carbene complexes, can solve the problems of difficulty in preparation and storage, unstable free carbene, easy self-polymerization, etc., and achieves high yield and cost. Inexpensive, well-tolerated results

Inactive Publication Date: 2012-02-15
ZHEJIANG UNIV
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AI Technical Summary

Problems solved by technology

The first method requires anhydrous and oxygen-free harsh conditions and special alkaline reagents, and many free carbenes are unstable and easy to self-polymerize
The second method requires the preparation of anhydrous metal acetates, metal alkoxides or metal amides, but these compounds are inherently difficult to prepare and store
The third method is relatively straightforward and simple. The disadvantage is that it needs to use expensive silver oxide reagents to prepare silver nitrogen heterocyclic carbene complexes, and silver nitrogen heterocyclic carbene complexes are often sensitive to light, and sometimes induce oxidation and degradation of carbene ligands.

Method used

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  • Method for synthesizing metal N-heterocyclic carbene complex
  • Method for synthesizing metal N-heterocyclic carbene complex
  • Method for synthesizing metal N-heterocyclic carbene complex

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Example 1 complex Pd-1 (C 20 h 21 f 12 N 7 P 2 Preparation of Pd)

[0040]

[0041] In a 50mL flask, add 826mg (1mmol) nickel nitrogen heterocyclic carbene complex Ni-1, 10mL acetonitrile solvent, 286mg (1mmol) (1,5-cyclooctadiene) palladium dichloride (Pd(COD)Cl 2 ), stirred and reacted for 8 hours in an oil bath at 60-70°C, filtered through a 300-mesh silica gel layer to obtain a colorless solution, concentrated to 3mL, added 15mL of diethyl ether to crystallize and the white powder obtained was the palladium nitrogen heterocyclic carbene complex Pd- 1. Purified by recrystallization to obtain 480 mg of colorless crystals, with a yield of 63%. 1 H NMR (400MHz, DMSO-d 6 ): δ8.97(d, J=4.8Hz, 1H, PyH), 8.58(br, 1H, PyH), 8.56(s, 1H, imidazolylidene H), 8.42(t, J=7.6Hz, 1H, PyH) , 8.40 (s, 1H, imidazolylidene H), 8.19 (d, J=8.0Hz, 1H, PyH), 8.18 (s, 1H, imidazolylidene H), 8.07 (t, J=7.8Hz, 1H, PyH), 7.88 (s, 1H, PyH), 7.73(t, J=6.0Hz, 1H, PyH), 7.57(s, 1H, imid...

Embodiment 2

[0042] Embodiment 2 complex Pd-2 (C 19 h 18 CIF 6 N 4 PPd) Preparation

[0043]

[0044] In a 50mL flask, add 953mg (1mmol) nickel nitrogen heterocyclic carbene complex Ni-2, 10mL acetonitrile, 571mg (2mmol) (1,5-cyclooctadiene) palladium dichloride (Pd(COD)Cl 2 ), in an oil bath at 50-60°C, stirred and reacted for 12 hours, filtered through a 300-mesh silica gel layer to obtain a yellow solution, concentrated to 3 mL, added 15 mL of ether to crystallize to obtain a yellow powder, which is the palladium nitrogen heterocyclic carbene complex Pd-2, Purified by recrystallization to obtain 1080 mg of yellow crystals with a yield of 92%. 1 H NMR (400MHz, DMSO-d 6 ): δ9.05(d, J=8.8Hz, 1H), 8.83(d, J=8.4Hz, 1H), 8.54(s, 2H, NCHCHN+phenanthroline H), 8.39(d, J=8.8Hz, 1H ), 8.14(s, 2H), 8.06(dd, J=8.0, J=5.2Hz, 1H), 7.82(d, J=2Hz, 1H, NCHCHN), 4.36(t, J=6.8Hz, 2H, NCHN 2 CH 2 CH 2 CH 3 ), 1.78 (m, 2H, NCH 2 CH 2 CH 2 CH 3 ), 1.33 (m, 2H, NCH 2 CH 2 CH 2 CH 3 ), 0.9...

Embodiment 3

[0045] Example 3 Complex Pd-3(C 20 h 22 f 12 N 6 P 2 Preparation of Pd)

[0046]

[0047] In a 50mL flask, add 695mg (1mmol) nickel nitrogen heterocyclic carbene complex Ni-3, 10mL acetonitrile, 286mg (1mmol) (1,5-cyclooctadiene) palladium dichloride (Pd(COD)Cl 2 ), stirred and reacted for 16 hours in an oil bath at 60-70°C, filtered through a 300-mesh silica gel layer to obtain a colorless solution, concentrated to 3 mL, added 15 mL of diethyl ether to crystallize to obtain a white powder, which is the palladium nitrogen heterocyclic carbene complex Pd-3 , and purified by recrystallization to obtain 640 mg of colorless crystals with a yield of 86%. 1 H NMR (400MHz, DMSO-d 6 ): δ8.29 (d, J=5.2Hz, 2H, 6-PyH), 8.24 (t, J=7.6Hz, 2H, 4-PyH), 7.96 (d, J=7.6Hz, 2H, 3-PyH ), 7.76(d, J=1.6Hz, 2H, NCHCHN), 7.62(t, J=6.4Hz, 2H, 5-PyH), 7.49(d, J=1.6Hz, 2H, NCHCHN), 6.17(d, J=14.8Hz, 2H, NCH 2 ), 5.80 (d, J=15.6Hz, 2H, NCH 2 ), 3.31 (s, 6H, NCH 3 ). 13 CNMR (100MHz, DMSO-d...

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Abstract

The invention discloses a method for synthesizing a metal N-heterocyclic carbene complex. The method comprises the following steps of: adding a nickel N-heterocyclic carbene complex and a metal precursor at a molar ratio of 1: (0.5-2) in an organic solvent such as acetonitrile, acetone or nitromethane, and reacting for 1-24 hours at the temperature of 35-70 DEG C; and after the reaction is completed, crystallizing and purifying so as to obtain the metal N-heterocyclic carbene complex. The method has the advantages of mild reaction conditions, simplicity in post-treatment and high yield; a cheap and available N-heterocyclic carbene complex is used so as to replace the traditional silver N-heterocyclic carbene complex to serve as a carbene transfer reagent, which is a further development for the synthesis method of the metal N-heterocyclic carbene complex, thus a foundation is laid for industrialized application of a transition metal N-heterocyclic carbene catalyst.

Description

technical field [0001] The invention relates to a method for synthesizing metal nitrogen heterocyclic carbene complexes. Background technique [0002] 1968 and Wanzlick independently published the first case of nitrogen heterocyclic carbene (NHCs) complexes. The two used basic metal compounds to deprotonate imidazolium salts to obtain imidazole-2-carbene complexes ( K.1, 3-Dimethyl-4-imidazolinyliden-(2)-pentacarbonylchrom einneuer übergangsmetall-carben-komplex. J. Organomet. Chem. 1968, 12, 42-43; Wanzlick, H.W.; Schonherr, H.J. Direct Synthesis of a Mercury Salt-Carbene Complex. Angew. Chem. 1968, 80, 154; Angew. Chem. Iht. Ed. Engl. 1968, 7, 141-142). In 1991, Arduengo et al. crystallized the first free nitrogen heterocyclic carbene (Arduengo III, A.J.; Harlow, R.L.; Kline, M.A stable crystalline carbene.J.Am.Chem.Soc.1991, 113, 361-363) , which stimulated widespread interest in the chemistry of free carbene and its metal complexes. In 1995, Herrmann et al. used ni...

Claims

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Application Information

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IPC IPC(8): C07F15/00C07F15/02C07F15/06C07F1/12C07F15/04C07D401/06C07D401/14C07D471/04C07D401/04C07D403/14B01J31/22C07C49/796C07C45/68C07F7/08C07C255/50C07C253/30
Inventor 陈万芝刘波
Owner ZHEJIANG UNIV
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