Synthesis, structures and electrochemical properties of amino-derivatives of diiron azadithiolates as active site models of Fe-only hydrogenase

被引:35
作者
Gao, WM
Liu, JH
Ma, CB
Weng, LH
Jin, K
Chen, CN
Åkermark, B
Sun, LC
机构
[1] Dalian Univ Technol, State Key Lab Fine Chem, Dalian 116012, Peoples R China
[2] Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Peoples R China
[3] Fudan Univ, Dept Chem, Shanghai 200433, Peoples R China
[4] Univ Stockholm, Arrhenius Lab, Dept Organ Chem, S-10691 Stockholm, Sweden
[5] Royal Inst Technol, KTH Chem, S-10044 Stockholm, Sweden
关键词
bioinorganic chemistry; catalysis; hydrogen production; iron-sulfur complex;
D O I
10.1016/j.ica.2005.10.053
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The preparation and characterization of two novel amino-incorporated sulfur-bridged dinuclear iron (I) complexes of the type [NR(mu-SCH2)2]Fe-2(CO)(6), one being amino protected [N(CH2CH2NHTs)(mu-SCH2)(2)]Fe-2(CO)(6) (8) and the other [(mu-SCH2)(2)Fe-2(-CO)(6)NCH2CH2N (mu-SCH2)(2)]Fe-2(CO)(6) (9) are described. These two complexes are readily prepared in a S(N)2 manner between double lithium anion and bis(chloromethyl) amine derivatives. The structures of 8 and 9 were characterized by IR, H-1, C-13 NMR, MS and HRMS spectra and further determined by X-ray analyses. Protonation of complex 8 gave the mono N-protonated product, while for 9 the protonation occurred in both of the N atoms. The redox properties were evaluated by cyclic voltammograms. It was shown that these two complexes can catalyze electrochemical reduction of proton to molecular hydrogen. (c) 2005 Elsevier B.V. All rights reserved.
引用
收藏
页码:1071 / 1080
页数:10
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