Oxidation of Substituted Iron Carbonyl Complexes in Acetonitrile, Acetone, and Dichloromethane at Mercury and Platinum Electrodes

S. W. Blanch, A. M. Bond, R. Colton

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Abstract

The oxidative electrochemistry of the substituted iron carbonyl complexes Fe(CO)4L and Fe(CO)3L2, where L is a monodentate tertiary phosphine, arsine, or stibine ligand, has been studied in acetone, dichloromethane, and acetonitrile at both Hg and Pt electrodes. At platinum electrodes, for L = AsPh3 or SbPh3 the initially generated 17-electron cations [Fe(CO)4L]+ and [Fe(CO)3L2]+ are unstable in all solvents while with phosphorus ligands the species [Fe(CO)3(PPh3)2]+ has some stability in dichloromethane. Reactions leading to decomposition are considered. In marked contrast, at mercury electrodes, the cations appear to be substantially more stable than at platinum, and chemically reversible behavior can be observed where the response is completely irreversible at platinum. The data are explained in terms of a chemically modified pathway at mercury electrodes giving rise to “mercury stabilized” cations.

Original languageEnglish
Pages (from-to)755-761
Number of pages7
JournalInorganic Chemistry
Volume20
Issue number3
DOIs
Publication statusPublished - Mar 1981
Externally publishedYes

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