Carboxylato‐Modified New Oxo‐Centred Triruthenium Cluster Compounds with CO and Solvent Ligands: The X‐ray Structure of [Ru3O(C2H5CO2)6(CO)(THF)2

Abstract

AbstractNew synthetic precursors for CO‐coordinated, oxo‐centred triruthenium(II,III,III) complexes with varied carboxylato groups [Ru3O(RCO2)6(CO)(solvent)2] where R = C2H5, CH3 and C6H5 have been prepared and characterised. Among the series, the propionato‐bridged complex [Ru3O(C2H5CO2)6(CO)(THF)2] (1) was structurally determined by single‐crystal X‐ray crystallography. Cyclic voltammetry revealed thatthe benzoato‐bridged complex [Ru3O(C6H5CO2)6(CO)(C2H5OH)2] in 0.1 mol dm–3 nBu4NPF6/DMF undergoes two consecutive one‐electron processes assignable to the redox of the Ru3(μ3‐O) core, the redox potentials of which are highly dependent on the electron‐donating/accepting nature of the carboxylato groups. UV‐light excitation of the compounds in CH3CN resulted in the dissociation of CO to form the tris(CH3CN) compounds [Ru3O(RCO2)6(CH3CN)3] (R = C2H5, CH3 and C6H5). These compounds are highly useful as synthetic precursors to a wide range of μ3‐oxo‐triruthenium derivatives with well‐defined redox responses. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)