New Dinuclear Asymmetric Complexes of Ruthenium and Rhenium

FAGALDE, FLORENCIA; KATZ, NÉSTOR E.

JOURNAL OF COORDINATION CHEMISTRY

Taylor & Francis

Lugar: Abingdon; Año: 2001 vol. 54 p. 367 - 377

0095-8972

New dinuclear asymmetric complexes of ruthenium and rhenium, of formula  [(bpy)(CO)3ReI(4,4'-bpy)RuII/III(NH3)5]3+/4+have been prepared and characterized by spectroscopic and electrochemical techniques. In the mixed-valent species [ReI, RuIII], the back electron transfer reaction RuII ® ReII , that occurs after light excitation, is predicted to be in the Marcus inverted region. This fact is consistent with the observed quenching of the luminiscence of the Re chromophore in [(bpy)(CO)3ReI(4,4'-bpy)RuIII(NH3)5]4+ , when compared to the parent complex [(bpy)(CO)3ReI(4,4'-bpy)]+. A theoretical treatment due to Creutz, Newton and Sutin has been successfully applied to predict the electronic coupling element in the mixed-valent complex.