Oxo transfer and metal oxidation in the reaction of [Ru(PPh3)3Cl2] with m-chloroperbenzoic acid: structure of [Ru(PPh3)2(m-ClC6H4CO2)Cl2]
Abstract
One mol and 0.5 mol of peracid are consumed for oxo transfer to PPh3 and oxidation of metal, respectively, in the reaction of [Ru(PPh3)3Cl2] with m-ClC6H4CO3H. The active oxo-transfer agent is metal-bound peracid. After oxo transfer the carboxylate residue remains chelated to the metal centre as shown by an X-ray structure determination of the product [Ru(PPh3)2(m-ClC6H4CO2)Cl2](1). The trans, cis, cis-RuP2O2Cl2 co-ordination sphere has two-fold symmetry. Its e.s.r. and near-i.r. spectra are in agreement with the energy order dxy > dxz′, dyz. The complex undergoes one-electron quasi-reversible reduction but only at low potentials (E298°–0.40 V vs. saturated calomel electrode).