Electrochemistry of phosphaferrocenes: II. Electrochemical behavior of 3,3′,4,4′-tetramethyl-1,1′- diphosphaferrocene bonded to M(CO)5 (M = Cr,Mo, W) fragments forming heterometallic complexes with multiple redox centers |
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Authors: | Paul Lemoine Maurice Gross Pierre Braunstein François Mathey Bernard Deschamps John H Nelson |
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Institution: | 1. Laboratoire d''Electrochimie et de Chimie Physique du Corps Solide Université Louis Pasteur, 4 rue Blaise Pascal, U.A. au CNRS No. 405, Strasbourg France;2. Laboratoire de Chimie de Coordination, U.A. au CNRS No. 416, Universite Louis Pasteur, 67070 Strasbourg Cedex, France;3. Equipe C.N.R.S./S.N.P.E., 94320 Thiais France |
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Abstract: | The redox behaviour of a series of heterometallic phosphaferrocenes (hereafter refered to as I, II and III) has been studied in propylene carbonate containing 0.1 M (C2H5)4N+ ClO4? both mercury and platinum electrodes.Complex I (DPF) undergoes a reversible one-electron reduction. Complexes II and III exhibit the same reversible reduction step and one (species II) or two (species III) additional irreversible reduction step(s) generating M(CO)5]? anions (M = Cr, Mo, W).Oxidation of the complexes II and III indicates that fragment I is involved in the first, easiest, oxidation step, whereas further step(s) involve the M(CO)5 moieties. The redox characteristics of the complexes I, II, III, clearly indicate the absence of cooperation between metallic centers in II and III and the very effective barrier provided by the central iron in moiety I towards mutual effects of both phospholyl rings. |
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