基于双齿膦配体的含Fe2S2大分子：合成、表征及催化电化学制氢

Bidentate phosphine ligand based Fe2S2-containing macromolecules: synthesis, characterization, and catalytic electrochemical hydrogen production.

作者信息

Gao Weiming, Liu Jianhui, Akermark Björn, Sun Licheng

机构信息

State Key Laboratory of Fine Chemicals, Dalian University of Technology, 116012 Dalian, People's Republic of China.

出版信息

Inorg Chem. 2006 Nov 13;45(23):9169-71. doi: 10.1021/ic061258e.

DOI:10.1021/ic061258e

PMID:17083211

Abstract

The reaction of [Fe2(CO)6(mu-SCH2)2NCH2CH2N(mu-SCH2)2Fe2(CO)6] (1) with 1,2-bis(diphenylphosphino)ethane in the presence of Me3NO.2H2O affords two structurally different metallomacromolecules: a dimer of the type [{Fe2(CO)5(mu-SCH2)2NCH2CH2N(mu-SCH2)2Fe2(CO)5}(Ph2PCH2)2] (2) and a tetramer species containing eight iron centers with an overall formula of [{Fe2(CO)6(mu-SCH2)2NCH2CH2N(mu-SCH2)2Fe2(CO)5}2(Ph2PCH2)2] (3). Their structures have been determined by X-ray crystallography, showing one macrocyclic complex (2) and one linear complex (3). Electrochemical hydrogen evolution catalyzed by these two complexes with ca. 80-90 single-run turnovers is observed, indicating good potential as catalysts for future applications.

摘要

[Fe2(CO)6(μ - SCH2)2NCH2CH2N(μ - SCH2)2Fe2(CO)6] (1) 在Me3NO·2H2O存在下与1,2 - 双(二苯基膦基)乙烷反应，生成两种结构不同的金属大分子：[{Fe2(CO)5(μ - SCH2)2NCH2CH2N(μ - SCH2)2Fe2(CO)5}(Ph2PCH2)2] (2) 类型的二聚体和一个含有八个铁中心的四聚体物种，其通式为[{Fe2(CO)6(μ - SCH2)2NCH2CH2N(μ - SCH2)2Fe2(CO)5}2(Ph2PCH2)2] (3)。它们的结构已通过X射线晶体学确定，显示出一个大环配合物(2)和一个线性配合物(3)。观察到这两种配合物催化电化学析氢反应，单次运行周转数约为80 - 9�，表明它们作为未来应用催化剂具有良好的潜力。