Chemically Significant Interactions Between Ruthenium Ions in Oxo-Bridged Complexes of Ruthenium(III).

摘要

A series of oxo-bridged complexes of ruthenium(III), has been prepared. The formulation of the complexes is based on the results of a variety of experiments, including elemental analyses, solution conductivity, and magnetism, and by their electron transfer properties. The chemical and electronic properties of the oxo-bridged dimers are unusual when compared to related bis(2,2-bipyridine) complexes of ruthenium. From electrochemical studies in acetonitrile, the ion ((bipy)2C1RuC1(bipy)2)(2+) can be oxidized to +4 and mixed-valence +3 (Ru(III)-Ru(IV)) ions and reduced to the mixed-valence (Ru(II)-Ru(III)) +1 ion. The +3 ion has been isolated as the salt ((bipy)2C1RuORuC1(bipy)2)(PF6)3, and the results of an ESCA study indicate that the two ruthenium ions equivalent. The chemical, spectral, and magnetic properties of the oxo-bridged ions can be interpreted by using a qualitative molecular orbital scheme, based on the assumption that strong, chemically significant interactions exist between the ruthenium ions through the bridging oxide ion ligand.