An Important Role of the One-Electron Reduction Nitrosyl Coordinated to Ruthenium. A Redox-Induced Oxygen Atom Transfer Reaction between the Nitrosyl and Adjacent Nitrite Moieties of {RuNO}7-Type Nitrosyl Complex

Abstract

Abstract A facile redox-induced nitrito-to-nitro isomerization occurs in cis-[Ru(NO)(ONO)(bpy)2]2+ ({RuNO}6-type nitrosyl, bpy = 2,2′-bipyridine). At room temperature, the one-electron reduction species (cis-[Ru(NO·)(ONO)(bpy)2]+({RuNO}7)) changes immediately to cis-[Ru(NO·)(NO2)(bpy)2]+ ({RuNO}7), which can be converted to cis-[Ru(NO)(NO2)(bpy)2]2+ ({RuNO}6) by one-electron oxidation. The nitro species is an isomeric twin of the original nitrito species. A mechanistic investigation has established that, during the nitrito–nitro redox-induced rearrangement, an oxygen-atom transfer reaction proceeded between the nitrosyl and the adjacent nitrite ligands. Such a behavior could not be found in the thermally-induced nitrito–nitro rearrangement of the {RuNO}6-type nitrosyl complex mentioned above. The {RuNO}7-type nitrosyl complex appears to behave as a key intermediate species of the oxygen-atom transfer reaction.