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Indexed by:期刊论文

Date of Publication:2004-09-20

Journal:CHEMISTRY-A EUROPEAN JOURNAL

Included Journals:Scopus、SCIE、EI、PubMed

Volume:10

Issue:18

Page Number:4474-4479

ISSN No.:0947-6539

Key Words:bioinorganic chemistry; cluster compounds; diiron azaditholate; iron only hydrogenase; redox chemistry

Abstract:Complex [{(mu-SCH(2))(2)N(4-NO(2)C(6)H(4))}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-SCH(2))(2)N(4-NH(2)C(6)H(4))}Fe(2)(CO)(6)] (5) in 67% yield. Both complexes were characterized by IR, (1)H and (13)C 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.