Abstract
The redox behavior of sandwich indenyl complexes of the general formula (η5-C9H7)ML (M=Ru and L=η5-C9H7 (1), η5-C5H5 (2), η5-C5Me5 (3); M=Os, L=η5-C9H7 (4)) has been studied in THF, MeCN, and CH2Cl2 by cyclic voltammetry and controlled potential electrolysis on a Pt electrode in the −85 to +20 °C temperature range. The title complexes have been found to undergo reversible one-electron oxidation to the corresponding radical cations, whose stabilities and reactivities depend on the nature of both the metal and °-ligands and of the nucleophilic properties of the solvent. The fast interaction of the electrogenerated 17-electron radical cations with nucleophiles yields bent sandwich 19-electron radical cations, [(η5-C9H7)M(L)(Nu)]+ (Nu = Cl−, MeCN, or THF), the latter undergoing one-electron oxidation to the corresponding [(η5-C9H7)M(L)(Nu)]2+ dications. In the case of Nu=THF, the reaction of the electrogenerated 17-electron radical cations with nucleophiles appears to be reversible. Radical cations [(η5-C9H7)2M]+· (M=Ru, Os) have been characterized by ESR spectra.
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