Synthesis, protonation and electrochemical properties of trinuclear NiFe2 complexes Fe-2(CO)(6)(mu(3)-S)(2)[Ni(Ph2PCH2)(2)NR] (R = n-Bu, Ph) with an internal pendant nitrogen base as a proton relay
Release Time:2019-03-10 Hits:
Indexed by: Journal Article
Date of Publication: 2009-01-20
Journal: INORGANICA CHIMICA ACTA
Included Journals: SCIE
Volume: 362
Issue: 2
Page Number: 372-376
ISSN: 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.