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论文类型：期刊论文

发表时间：2008-04-28

发表刊物：DALTON TRANSACTIONS

收录刊物：SCIE、EI、PubMed

期号：16

页面范围：2128-2135

ISSN号：1477-9226

摘要：Three N-substituted selenium-bridged diiron complexes [{(mu-SeCH2)(2)NC6H4R}Fe-2(CO)(6)] (R= 4-NO2, 7; R = H, 8; R = 4-CH3, 9) were firstly prepared as biomimetic models for the Fe-Fe hydrogenases active site. Models 7-9 could be generated by the convergent reaction of [(mu-HSe)(2)Fe-2(CO)(6)] (6) with N,N-bis(hydroxymethyl)-4-nitroaniline ( 1), N, N-bis( hydroxymethyl) aniline ( 2), and N, N-bis( hydroxymethyl)-4-methylaniline ( 3) in 46-52% yields. All the new complexes 7-9 were characterized by IR, H-1 and C-13 NMR and HRMS spectra and their molecular structures were determined by single-crystal X-ray analysis. The redox properties of 7-9 and their dithiolate analogues [{(mu-SCH2)(2)NC6H4R}Fe-2(CO)(6)] (R= 4-NO2, 7s; R = H, 8s; R = 4-CH3, 9s) were evaluated by cyclic voltammograms. The electrochemical proton reduction by 9 and 9s were investigated in the presence of p-toluenesulfonic acid (HOTs) to evaluate the influence of changing the coordinating S atoms of the bridging ligands to Se atoms on the electrocatalytic activity for proton reduction.