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Ligand Effect on the Electrochemical Oxidation of trans -[Ru(NO2)X(py)4] n ( n = 0 for X = NO2, n = + for X = NH3). Reactivity of Coordinated Nitro (RuII–NO2) to Give Monooxygen Moiety (RuIV=O) Depends on the Ambient Ligand (X)

1993; Oxford University Press; Volume: 66; Issue: 5 Linguagem: Inglês

10.1246/bcsj.66.1397

1348-0634

Noriharu Nagao, Hirotaka Nagao, H. NISHIMURA, Hiroshi Kuroda, Katsuyuki Satoh, F. Scott Howell, Masao Mukaida,

Lanthanide and Transition Metal Complexes

Abstract The electrochemical behavior of trans-[Ru(NO2)X(py)4]n(n = 0 for X = NO2 and n = + for NH3) in CH3CN was investigated at various temperatures. trans-[RuII(NO2)2(py)4] undergoes a one-electron oxidation to give trans-[RuIII(NO2)2(py)4]+. Rapid chemical reactions (nitro–nitrito isomerization, dimeric intermediate formation, and its disintegration) follow in succession until nearly equal amounts of trans-[Ru(NO)(NO2)(py)4]2+ and trans-[RuII(NO2)(solvent)(py)4]+ are generated as the final products. Essentially the same result was found in trans-[Ru(NO2)(NH3)(py)4]+. These results were quite different from those observed previously in the electrochemical oxidation of trans-[RuIICl(NO2)(py)4], where both trans-[RuIVCl(O)(py)4]+ and trans-[Ru(NO)Cl(py)4]2+ were generated directly by one-electron oxidation. We conclude that the different electrochemical behavior between trans-[RuCl(NO2)(py)4] and trans-[Ru(NO2)X(py)4]n (X = NO2 and NH3) stems primarily from a different disintegration mode of the above-mentioned dimeric intermediate species.