Synthesis, structures and electrochemical properties of nitro- and amino-functionalized diiron azadithiolates as active site models of Fe-only hydrogenases

被引:96
作者
Liu, TB
Wang, M
Shi, Z
Cui, HG
Dong, WB
Chen, JS
Akermark, B
Sun, LC
机构
[1] Dalian Univ Technol, State Key Lab Fine Chem, Dalian 116012, Peoples R China
[2] Jilin Univ, Key Lab Inorgan Synth & Preparat Chem, Changchun 130023, Peoples R China
[3] Stockholm Univ, Arrhenius Lab, Dept Organ Chem, S-10691 Stockholm, Sweden
关键词
bioinorganic chemistry; cluster compounds; diiron azaditholate; iron only hydrogenase; redox chemistry;
D O I
10.1002/chem.200400004
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Complex [{(mu-SCH2)(2)N(4-NO2C6H4)}Fe-2(CO)(6)] (4) was prepared by the reaction of the dianionic intermediate [(mu-S)(2)Fe-2(CO)(6)](2-) and N,N-bis(chloromethyl)-4-nitroaniline as a biomimetic model of the active site of Fe-only hydrogenase. The reduction of 4 by Pd-C/H-2 under a neutral condition afforded complex [{(mu-SCH2)(2)N(4-NH2C6H4)}Fe-2(CO)(6)] (5) in 67% yield. Both complexes were characterized by IR, H-1 and C-13 NMR spectroscopy and MS spectrometry. The molecular structure of 4, as determined by X-ray analysis, has a butterfly 2Fe2S core and the aryl group on the bridged-N atom slants to the Fe(2) site. Cyclic voltammograms of 4 and 5 were studied to evaluate their redox properties. It was found that complex 4 catalyzed electrochemical proton reduction in the presence of acetic acid. A plausible mechanism of the electrocatalytic proton reduction is discussed.
引用
收藏
页码:4474 / 4479
页数:6
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