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Indexed by:期刊论文

Date of Publication:2009-01-20

Journal:INORGANICA CHIMICA ACTA

Included Journals:SCIE

Volume:362

Issue:2

Page Number:372-376

ISSN No.:0020-1693

Key Words:Electrochemistry; Heteronuclear complex; Hydrogenase; Diphosphine ligand; Protonation

Abstract:Two trinuclear NiFe2 complexes Fe-2(CO)(6)(mu(3)-S)(2)[Ni(Ph2PCH2)(2)NR] (R = n-Bu, 1; Ph, 2) containing an internal base were prepared as biomimetic models for the active sites of FeFe and NiFe hydrogenases. Treatment of complex Fe-2(CO)(6)(mu(3)-S)(2)[Ni(Ph2PCH2)(2)N(n-Bu)] (1) with HOTf gave an N-protonated complex [Fe-2(CO)(6)(mu(3)-S)(2){Ni(Ph2PCH2)(2)NH(n-Bu)}][OTf] ([1H][OTf]). The structures of complexes 1, 2 and [1H][OTf] were determined by X-ray crystallography, which shows that the proton held by the N atom of [1H][OTf] lies in an equatorial position. Cyclic voltammograms of complexes 1 and [1H][OTf] were studied and compared with that of Fe-2(CO)(6)(mu(3)-S)(2)[Ni(dppe)]. (C) 2008 Elsevier B.V. All rights reserved.