Abstract
AbstractThe reaction of [(Ind)Ru(dppf)Cl] (Ind = η5‐C9H7) (2) with RSNa {R = Me, Et, Ph, Ph2P(CH2)2} proceeds in MeOH to give [(Ind)Ru(dppf)(SR)] {R = Me (3), Et (4), Ph (5), Ph2P(CH2)2 (7)}, as well as [(Ind)Ru(dppf)H] (6), in all cases except for R = Ph. This R‐dependence of the product mixture was rationalised on a RS–/MeOH ↔ MeO–/RSH equilibrium involving the interaction of thiolate (RS–) with MeOH, and the relative nucleophilicities of RS– versus MeO–; 6 arose from β‐H elimination from an OMe derivative. Cyclic voltammetric measurements on 2, 3, 4 and 5, as well as the Cp (η5‐C5H5) and Cp* (η5‐C5Me5) analogues of 2, indicated that the formal oxidation potentials for [LRu(dppf)Cl] complexes {L = Ind (2), Cp (2A) and Cp* (2B)} occurred in the order Cp* < Ind < Cp, correlating with the more electron‐donating groups lowering the oxidation potentials. EPR experiments performed on the one‐electron oxidised forms of 3 and 5 indicated paramagnetic compounds with g values close to 2, while the two‐electron oxidised forms of 3 and 5 were diamagnetic. All the complexes were characterised spectroscopically, and 5 and 6 also crystallographically. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
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