An approach to water-soluble hydrogenase active site models: Synthesis and electrochemistry of diiron dithiolate complexes with 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane ligand(s)

被引:61
作者
Na, Yong
Wang, Mei
Jin, Kun
Zhang, Rong
Sun, Licheng
机构
[1] Dalian Univ Technol, State Key Lab Fine Chem, DUT, KTH Joint Educ & Res Ctr Mol Devices, Dalian 116012, Peoples R China
[2] Royal Inst Technol, KTH, Dept Chem, S-10044 Stockholm, Sweden
基金
中国国家自然科学基金;
关键词
biomorganic chemistry; diiron dithiolate complexes; electrochemistry; iron-only hydrogenase; triazaphosphaadamantane ligand;
D O I
10.1016/j.jorganchem.2006.08.082
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
In order to improve the hydro- and protophilicity of the active site models of the Fe-only hydrogenases, three diiron dithiolate complexes with DAPTA ligand(s) (DAPTA=3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonanc), (mu-pdt)[Fe(CO)(2)][Fe(CO)(2)(DAPTA)] (1, pdt = 1,3-propanedithiolato), (mu-pdt)[Fe(CO)(2)(DAPTA)](2) (2) and (mu-pdt)[Fe(CO)(2)(PTA)][Fe(CO)(2)(DAPTA)] (3), were prepared and spectroscopically characterized. The water solubility of DAPTA-coordinate complexes 1-3 is better than that of the PTA-coordinate analogues. With complexes 1-3 as electrocatalysts, the overvoltage is reduced by 460-770 mV for proton reduction from acetic acid at low concentration in CH3CN. Significant decrease, up to 420 mV, in reduction potential for the Fe(I)Fe(I) to Fe(I)Fe(0) process and the curve-crossing phenomenon are observed in cyclic voltammograms of 2 and 3 in CH3CN/H2O mixtures. The introduction of the DAPTA ligand to the diiron dithiolate model complexes indeed makes the water solubility of 2 and 3 sufficient for electrochemical studies in pure water, which show that the proton reduction from acetic acid in pure water is electrochemically catalyzed by 2 and 3 at ca. -1.3 V vs. NHE. (c) 2006 Elsevier B.V. All rights reserved.
引用
收藏
页码:5045 / 5051
页数:7
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