Synthesis, crystal structures and electrocatalytic properties of bridgehead-C-functionalized diiron dithiolate complexes

被引：23

作者：

Zhao, Pei-Hua ^{[1
]}

Xiong, Kuan-Kuan ^{[1
]}

Liang, Wen-Jun ^{[1
]}

Hao, Er-Jun ^{[2
]}

机构：

[1] North Univ China, Sch Mat Sci & Engn, Res Ctr Engn Technol Polymer Composites Shanxi Pr, Taiyuan, Peoples R China

[2] Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang, Peoples R China

来源：

JOURNAL OF COORDINATION CHEMISTRY | 2015年 / 68卷 / 06期

基金：

中国国家自然科学基金;

关键词：

Diiron dithiolate complexes; Bridgehead-C-functionalized; Synthesis; Crystal structure; Electrocatalytic property; ACTIVE-SITE; IRON HYDROGENASE; PROPANEDITHIOLATE; RELEVANT; CATALYSIS; MODEL; EVOLUTION; CLUSTERS;

D O I：

10.1080/00958972.2014.1002398

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

To investigate the influence of bridgehead-C functionality in diiron dithiolate complexes on the molecular structure and electrocatalytic properties of [FeFe]-hydrogenase models, three new bridgehead-C-functionalized model complexes 1-3 have been synthesized and structurally characterized. Treatments of parent complex [(-SCH2)(2)CHCO2H][Fe-2(CO)(6)] (A) with the esterification agents o-MeC6H4OH, p-ClC6H4OH, or p-HOC6H4CHO in the presence of 4-dimethylaminopyridine and dicyclohexylcarbodiimide in CH2Cl2 at room temperature resulted in formation of [(-SCH2)(2)CHCO2R][Fe-2(CO)(6)] (R=o-MeC6H4-, 1; p-ClC6H4-, 2; p-OHCC6H4-, 3) in 53-55% yields. The new complexes 1-3 were characterized by elemental analysis, IR and NMR spectroscopy, and especially determined by X-ray crystallography. The electrochemical properties of 1-3 and the electrocatalytic H-2 evolution catalyzed by 1 have been investigated by cyclic voltammetry, where 1 is a catalyst for HOAc proton reduction to H-2 under electrochemical conditions.

引用

页码：968 / 979

页数：12

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