Preparation, Structure and Electrochemical Property of a Pyrazole-substituted Diiron Dithiolate Complex  

作　　者：冯亚南 陈瑞平 李志华 杜少武 

机构地区：[1]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences [2]Graduate School of Chinese Academy of Sciences

出　　处：《Chinese Journal of Structural Chemistry》2012年第11期1650-1656,共7页结构化学（英文）

基　　金：supported by the National Basic Research Program of China(973Program,2012CB821702);the National Natural Science Foundation of China(21173221and20903096);the State Key Laboratory of Structural Chemistry(20120015)

摘　　要：A pyrazole-substituted diiron dithiolate complex [Fez（p-pdt）（CO）5（3,5-Me2Pz）] （1, 3,5-MezPz = 3,5-dimethylpyrazole） was prepared as a biomimetic model for the active site of [FeFe]-hydrogenase by CO-substitution of aU-carbonyl complex [Fe2（μ-pdt）（CO）6] with 3,5-Me2Pz. The molecular structure was confirmed by MS, IR, 1H NMR, elemental analysis and single-crystal X-ray analysis. Complex 1 crystallizes in the triclinic system, space group PI with a = 9.108（7）, b = 9.743（8）, c = 11.192（9）A, a = 109.235（5）, fl = 101.914（9）, y = 96.605（6）. In CH3CN solution, reversible transformation between 1 and the acetonitrile-substituted species [Fe2（p-pdt）- （CO）5（NCCH3）] was detected by both IR and cyclic voltammetry （CV）. The electrochemical proton reduction catalyzed by 1 in the presence of acetic acid was also studied in CH2C12.A pyrazole-substituted diiron dithiolate complex [Fez（p-pdt）（CO）5（3,5-Me2Pz）] （1, 3,5-MezPz = 3,5-dimethylpyrazole） was prepared as a biomimetic model for the active site of [FeFe]-hydrogenase by CO-substitution of aU-carbonyl complex [Fe2（μ-pdt）（CO）6] with 3,5-Me2Pz. The molecular structure was confirmed by MS, IR, 1H NMR, elemental analysis and single-crystal X-ray analysis. Complex 1 crystallizes in the triclinic system, space group PI with a = 9.108（7）, b = 9.743（8）, c = 11.192（9）A, a = 109.235（5）, fl = 101.914（9）, y = 96.605（6）. In CH3CN solution, reversible transformation between 1 and the acetonitrile-substituted species [Fe2（p-pdt）- （CO）5（NCCH3）] was detected by both IR and cyclic voltammetry （CV）. The electrochemical proton reduction catalyzed by 1 in the presence of acetic acid was also studied in CH2C12.

关 键 词：bioinorganic chemistry [FeFe]-hydrogenase SUBSTITUTION proton reduction 

分 类 号：O627.8[理学—有机化学]