Influence of tertiary phosphanes on the coordination configurations and electrochemical properties of iron hydrogenase model complexes: Crystal structures of [(mu-S2C3H6)Fe-2(CO)(6-n)L-n] (L = PMe2Ph, n=1, 2; PPh3 P(OEt)(3), n=1)
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Indexed by: Journal Article
Date of Publication: 2005-06-20
Journal: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Included Journals: Scopus、SCIE
Issue: 12
Page Number: 2506-2513
ISSN: 1434-1948
Key Words: binuclear iron complexes; bioinorganic chemistry; carbonyl displacement; Fe-only hydrogenase; P ligands
Abstract: A series of mono- and disubstituted diiron complexes [(mu-pdt)-Fe-2(CO)(5)L] [pdt = 1,3-propanedithiolato; L = PMe3 (2), PMe2Ph (3), PPh3 (4), P(OEt)(3) (5)] and [(mu-pdt)Fe-2(CO)(4)L-2] [L = PMe2Ph (6), PPh3 (7), P(OEt)3 (8)] were prepared as Fe-only hydrogenase-active-site models by controllable CO displacement of [(mu-pdt)Fe-2(CO)(6)] by tertiary phosphanes. The coordination configurations of 3-6 were characterized by X-ray crystallography. Disubstituted diiron complex 6 features an apical/apical coordination mode, instead of the typical transoid basal/basal configuration. The electrochemistry of 2-6 and 8 was studied by cyclic voltammetry to evaluate the effects of different tertiary phosphane ligands on the redox properties of the iron atoms of model complexes. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)