Electrochemical oxidation of rhenium alkyl complexes of the formula (.eta.5-C5H5)Re(NO)(PPh3)(R): evidence for one-electron charge transfer
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The redox properties of rhenium alkyl complexes R-(Re) ((Re) = (r5-C5H5)Re(NO)(PPh3)) with R = PhCH2(1), (CH3)2CHCH2(2), and Ph(CH3)CH (3) are studied electrochemically. Cyclic voltammetric, peak current, heterogeneous charge transfer, and chronoamperometric studies in a variety of solvents indicate that 1–3 undergo initial one-electron oxidation to cation radicals R-(Re)*+. These decompose by an EC mechanism at rates that correlate with solvent donor ability. Intermediates, possibly R-(Re/solvent) R+, are detected by cyclic voltammetry. Coulometric experiments further suggest that R-(Re),+can catalytically oxidize solvent via R-(Re/solvent)'+. These data contrast with an earlier report describing evidence for a two-electron oxidation of 3. © 1987, American Chemical Society. All rights reserved.
author list (cited authors)
Bodner, G. S., Gladysz, J. A., Folmer Nielsen, M., & Parker, V. D.