Electrochemical behaviour and chemical oxidation study of the thio- and phosphido-bridge binuclear iron complexes |
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| Authors: | R Mathieu R Poilblanc P Lemoine M Gross |
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| Institution: | Laboratoire de Chimie de Coordination, B.P. 4142, 31030 Toulouse Cédex France;Laboratoire d''Electrochimie et de Chimie Physique du Corps Solide, E.R.A. au No. 468, 4, rue Blaise Pascal, 67000 Strasbourg France |
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| Abstract: | The electrochemical behaviour of thio and phosphido complexes of iron(I): Fe2XY(CO)6nLn (X = Y = SR, PR2 and X = SR, Y = PR2, L = PR3) has been studied on platinum and mercury electrodes, in organic solvent. These complexes are reduced in a two-electron irreversible process. A large difference is observed between their oxidation potentials on mercury and platinum electrodes; this is ascribed to the formation of a mercury complex in which mercury is inserted into the metalmetal bond. In oxidation on platinum electrodes, two mono-electronic waves are observed. The influece of the ligand basicity on the cathodic E values is discussed. A parallel shift is observed between the E and the IR ν(CO) of the totally symmetrical mode. Chemical oxidation of the complexes shows that the dications cannot be isolated, and leads to isolation of the following species: FeP(CH3)2(CO)3]2AgNO3, FeSCH3(CO)2P(CH3)3]2(NO3)2, {FeSCH3(CO)2P(CH3)3]2F} PF6, where NO3? and F? act as ligands. |
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