Intramolecular, outer-sphere electron transfer in the mixed-valence ion [(bpy)2ClRu(Ph2PCH2PPh 2)RuCl(bpy)2]3+

Article abstract of DOI:10.1021/ic50205a034

The synthesis of the μ-diphosphine-bridged dimer [(bpy)₂ClRu(Ph₂PCH₂PPh ₂)RuCl(bpy)₂]X₂ (bpy = 2,2′-bipyridine, X = ClO₄ or PF₆) and its mixed-valence form is described. The mixed-valence 3+ ion has a low-intensity intervalence transfer (IT) transition in the near-infrared spectral region. The appearance of the band is of importance since, given the nature of the bridging ligand, it apparently represents an example of an outer-sphere intervalence transfer transition. The solvent dependence of the IT band energy is in agreement with results obtained for intramolecular IT transitions and with a dielectric continuum treatment for the solvent. The appearance of the IT transition allows the mixed-valence ion to act as a useful model for related outer-sphere electron-transfer reactions.