Behaviors of the one-electron reduction species of {RuNO}(6)-type complexes. An oxygen-transfer reaction occurs in the nitrosyl site of cis-[Ru(NO center dot)X(bpy)(2)](n+) (X = ONO2 for n = 1, X = CH3CN, H2O for n = 2) ({RuNO}(7)-type) to give an identical nitro species
M. Mukaida et al., Behaviors of the one-electron reduction species of {RuNO}(6)-type complexes. An oxygen-transfer reaction occurs in the nitrosyl site of cis-[Ru(NO center dot)X(bpy)(2)](n+) (X = ONO2 for n = 1, X = CH3CN, H2O for n = 2) ({RuNO}(7)-type) to give an identical nitro species, B CHEM S J, 73(1), 2000, pp. 85-95
Degradation sequences of cis-[Ru(NO.)X(bpy)(2)](n+) (X = ONO2, OCHO, OCOMe,
NO2, Cl for n = 1; X = CH3CN, H2O for n = 2) ({RuNO}(7)-type), a one-elect
ron reduction species of {RuNO}(6)-type complexes, were investigated in CH3
CN by monitoring using electrochemical techniques (both cyclic and hydrodyn
amic voltammetries). The results show that an oxygen transfer occurs effect
ively at the nitrosyl site of cis-[Ru(NO.)X(bpy)(2)](n+) (X = ONO2 for n =
1, X = CH3CN, H2O for n = 2) to give identical nitro species, cis-[Ru(NO2)(
CH3CN)(bpy)(2)](+). The extent that the nitrosyl-to-nitro conversion procee
ded, however, differs depending on the X ligands; X = CH3CN and H2O complex
es gave the nitro species in almost 40% yield, while X = ONO2 complex affor
ded nearly 80%. The monitoring results of the degradation sequences, along
with the differences in yields, suggest that different processes are operat
ing separately in the oxygen-transfer reaction. We propose some possible pr
ocesses for both reactions, although a further investigation is needed for
a detailed explanation.