N,N-coordination dimeric rhodium (II) complex as well as preparation method and application thereof

A complex, dimerized rhodium technology, applied in the preparation of organic compounds, organic compound/hydride/coordination complex catalysts, organic chemical methods, etc., to achieve the effect of good catalytic efficiency and high catalytic activity

Inactive Publication Date: 2012-07-04
XINJIANG TECHN INST OF PHYSICS & CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] In 1965, after O, O-coordinated dimeric rhodium (II) complex rhodium dipolyformate was first reported, in 1983, N, O-coordinated dimeric rhodium (II) complex dipolytrifluoroacetamide rhodium appeared. Back-to-back in 1985, Bear et al. reported N, N-coordination dimer rhodium (II) complexes N, N-diphenylbenzamidine rhodium Rh2 (dpba) 4, later chemists prepared different types of N,N-coordinated dimeric rhodium(II) complexes, and studied their crystal structure and electrochemical performance, in which only 1,8-naphthyridine is the ligand of N,N-coordinated rhodium(II) cations type complex bis-naphthyridine rhodium fluoroborate [Rh 2 (Napt) 4 ]·4BF 4 In addition to the silylation reaction of alkynes, for other N, N-coordinated rhodium (II) complexes, there are no reports that can be applied to catalytic chemical reactions

Method used

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  • N,N-coordination dimeric rhodium (II) complex as well as preparation method and application thereof
  • N,N-coordination dimeric rhodium (II) complex as well as preparation method and application thereof
  • N,N-coordination dimeric rhodium (II) complex as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Ligand preparation:

[0054] Preparation of N-(2-pyrrolidinyl)-methylsulfonylimide

[0055] In a 25 mL two-necked flask, 2-methoxy-1-pyrpyrrolidine (0.99 g, 10.0 mmol), methylsulfonamide (0.71 g, 7.5 mmol) and isopropanol (15 mL) were added, and the mixture was stirred And reflux for 24 hours, the solvent was evaporated under reduced pressure, and the residue was recrystallized from THF to obtain 1.05 g of white solid with a yield of 90%;

[0056] mp=144-145°C; 1 H NMR (400MHz, CDCl 3 )δ7.73(br s, 1H), 3.60(t, J=7.1Hz, 2H), 2.98(s, 3H), 2.69(t, J=7.6Hz, 2H), 2.13-2.05(m, 2H) ; 13 C NMR (100MHz, CDCl 3 )δ170.80, 46.62, 41.95, 33.23, 19.86. HRMS (ESI) C 5 h 10 N 2 NaO 2 S, measured value (calculated value) [(M+Na)+]: 185.0358 (185.0355);

[0057] Synthesis of Complex I:

[0058] Connect a Soxhlet extractor and a condenser to a 25mL two-necked round-bottom flask, add 4.0 g of a mixture of quartz sand and dry anhydrous sodium carbonate at a weight ratio of 1.5:3....

Embodiment 2

[0061] Ligand preparation:

[0062] Preparation of N-(2-pyrrolidinyl)-4-methylbenzenesulfonimide

[0063] In a 25 mL two-necked flask, 2-methoxy-1-pyrrolidine (0.99 g, 10.0 mmol), 4-methylbenzenesulfonamide (1.3 g, 7.5 mmol) and isopropanol (15 mL) were added, and the mixture Stirring and reflux reaction for 24 hours, the solvent was evaporated under reduced pressure, and the residue was recrystallized from ethyl acetate to obtain 1.5 g of white solid with a yield of 86%;

[0064] mp=149-150°C; 1 H NMR (400MHz, CDCl 3 )δ8.00(br s, 1H), 7.81(d, J=8.2Hz, 2H), 7.28(d, J=8.2Hz, 2H), 3.60(t, J=7.2Hz, 2H), 2.69(t , J=8.1Hz, 2H), 2.41(s, 3H), 2.11-2.03(m, 2H); 13 C NMR (100MHz, CDCl 3 )δ171.51, 142.68, 139.50, 129.32, 126.40, 46.37, 32.90, 21.48, 20.01.HRMS(ESI)C 11 h 14 N 2 NaO 2 S measured value (calculated value) [(M+Na) + ]: 261.0675(261.0668);

[0065] Synthesis of Complex II:

[0066] Connect a Soxhlet extractor and a condenser to a 25mL two-necked round-bottom flas...

Embodiment 3

[0069] Ligand preparation:

[0070] Preparation of N-(2-pyrrolidinyl)-4-methoxybenzenesulfonimide

[0071] In a 25mL two-necked flask, add 2-methoxy-1-pyrrolidine (0.99g, 10.0mmol), 4-methoxybenzenesulfonamide (1.4g, 7.5mmol) and isopropanol (15mL), and The mixture was stirred and refluxed for 24 hours, the solvent was evaporated under reduced pressure, and the residue was recrystallized from ethyl acetate to obtain 1.53 g of a white solid with a yield of 82%;

[0072] mp=146-147°C; 1 H NMR (400MHz, CDCl 3 )δ8.04(br s, 1H), 7.85(d, J=8.9Hz, 2H), 6.94(d, J=8.9Hz, 2H), 3.85(s, 3H), 3.59(t, J=7.1Hz , 2H), 2.69(t, J=8.0Hz, 2H), 2.13-1.99(m, 2H); 13 CNMR (100MHz, CDCl 3 )δ171.07, 162.66, 134.47, 128.65, 114.09, 55.76, 46.72, 33.34, 20.14. HRMS (ESI) C 11 h 14 N 2 NaO 3 S measured value (calculated value) [(M+Na) + ]: 277.0623(277.0617);

[0073] Synthesis of Complex III:

[0074] Connect a Soxhlet extractor and a condenser to a 25mL two-necked round-bottom flask, add 4....

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Abstract

The invention relates to an N, N-coordination dimeric rhodium (II) complex as well as a preparation method and application of the complex. The dimeric rhodium (II) complex is obtained through a ligand exchange reaction between N-(2- pyrrolidinyl) sulfimide compounds and rhodium acetate dimer. The complex has the advantages of a novel structure, easy available synthetic raw materials and a simple reaction operation. The complex shows good catalytic activity in a benzyl oxidizing reaction.

Description

technical field [0001] The invention relates to a metal-organic complex, in particular to a series of N,N-coordinated dimeric rhodium (II) complexes, a preparation method and an application in the field of benzylic oxidation reaction. Background technique [0002] Dimeric rhodium Rh(II) compound plays an important role in organometallic compounds. Due to its unique rigid structure, it has a wide range of applications in the fields of organometallic catalysis, anticancer metal drugs, phototherapy, photochemistry and supramolecular design. At present, dimeric Rh(II) complexes are widely used in carbon carbene-based, insertion reactions, cyclopropanation reactions, ylide reactions, cycloaddition reactions and nitrogen-carbene-based C-H amination reactions and free radical oxidation / reduction reaction, etc. [0003] In 1965, after O, O-coordinated dimeric rhodium (II) complex rhodium dipolyformate was first reported, in 1983, N, O-coordinated dimeric rhodium (II) complex dipol...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/00B01J31/22C07B41/06C07B41/08C07C205/45C07C201/12
Inventor 阿不都热合曼・乌斯曼夏热帕提・吐孙卢崇道
Owner XINJIANG TECHN INST OF PHYSICS & CHEM CHINESE ACAD OF SCI
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