Journal
INORGANICA CHIMICA ACTA
Volume 300, Issue -, Pages 661-667Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/S0020-1693(99)00571-X
Keywords
catalytic hydrocarbon oxygenation; ruthenium-pyridylamine complexes; alkyl hydroperoxides; electron-transfer reaction
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The use of TBHP (t-butyl hydroperoxide) or CHP (cumene hydroperoxide) with bis-mu-chloro Ru(II) dimers, [(RuCl)-Cl-II(L)](2)(ClO4)(2) (L = tris(2-pyridylmethyl)amine and tris(5-methyl-2-pyridylmethyl)amine), gave catalytic alkane and alkene oxygenation at 40 degrees C. These reactions were found to proceed via a Haber-Weiss-type electron-transfer reaction to generate alkoxo (RO.) and alkylperoxo (ROO.) radicals as reactive species. This electron transfer was mainly governed by the redox potentials of a complex employed as a catalyst. In addition, the environment around a ruthenium center(s) involving steric hindrance due to substituents on the pyridine rings and an intramolecular pi-pi interaction, should be also significant to regulate the reactivity of the catalyst; probably in terms of shielding of the ruthenium center(s) against the approach of peroxides to undergo the electron transfer. For those reactions with alkyl hydroperoxides, O-2 generated from peroxide decomposition plays an important role in promoting reactions as a radical chain carrier. (C) 2000 Elsevier Science S.A. All rights reserved.
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