Reactivity of 17- and 19-electron organometallic complexes. Formation of bent sandwich 19-electron radical cation complexes of ruthenium and osmium |
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Authors: | Kukharenko S. V. Strelets V. V. Denisovich L. I. Peterleitner M. G. Kreindlin A. Z. Kudinov A. R. Rybinskaya M. I. |
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Affiliation: | (1) Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences, 142432 Chernogolovka, Moscow Region, Russian Federation;(2) A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813 Moscow, Russian Federation |
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Abstract: | The redox behavior of sandwich indenyl complexes of the general formula (5-C9H7)ML (M=Ru and L=5-C9H7 (1), 5-C5H5 (2), 5-C5Me5 (3); M=Os, L=5-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, [(5-C9H7)M(L)(Nu)]+ (Nu = Cl–, MeCN, or THF), the latter undergoing one-electron oxidation to the corresponding [(5-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 [(5-C9H7)2M]+· (M=Ru, Os) have been characterized by ESR spectra.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2394–2399, December, 1995. |
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Keywords: | ruthenium and osmium complexes cyclic voltammetry electrochemical reactions |
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