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Electrochemical behaviour and chemical oxidation study of the thio- and phosphido-bridge binuclear iron complexes

1979; Elsevier BV; Volume: 165; Issue: 2 Linguagem: Inglês

10.1016/s0022-328x(00)94326-2

1872-8561

R. Mathieu, R. Poilblanc, P. Lemoine, M. Groß,

Electrochemical sensors and biosensors

The electrochemical behaviour of thio and phosphido complexes of iron(I): Fe2XY(CO)6nLn (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 metalmetal bond. In oxidation on platinum electrodes, two mono-electronic waves are observed. The influece of the ligand basicity on the cathodic E12 values is discussed. A parallel shift is observed between the E12 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.