| Budget Amount *help |
¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 1998: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1997: ¥2,700,000 (Direct Cost: ¥2,700,000)
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| Research Abstract |
The reaction between [Ru(NO)(H_2O)bpy_2]^<3+>({RuNO}^6) and formic acid gives [{Ru(mu-NO)}_2(bpy)_4]^<2+>, along with some other products species : cis-[Ru(NO)(OCHO)(bpy)_2]^<2+>([RuNO]^6) and cis-[Ru(OCHO)H_2O](bpy)_2]^+]. Structures of both complexes were confirmed by X-ray structure determination. The mu-nitrosyl complex consists of two cis-Ru(bpy)_2 fragments connected by two formally negatively charged bridging nitrosyl ligands. Electrochemical study of the complex shows that two successive one-electron oxidation wave to give[{Ru(mu-NO)}_2(bpy)_4]^<4+>({RuNO}^7-{RuNO}^7) are found. The generated two-electron oxidation species is disintegrated to afford a one-electron reduction species, cis-[Ru(NO^2)(CH_3CN)(bpy)_2]^<2+>({RuNO}^7), along with a small amount of an anexpected nitro species, cis-[Ru(NO_2)(CH_3CN)(bpy)_2]^+ this is the first observation which shows that the electrochemically induced nitrosyl-to-nitro conversion occurs in {RuNO}^7 type complex. The characteristics of electrochemicafly generated one-electron reduction species, cis-[Ru(NO^*)(x)(bpy)_2]^<(n-1)>, ({RuNO}^7) (x=H_2O,CH_3CN,ONO_2, NO_2, ONO, OCHO, OCOMe, Cl) were investigated in the connections. Among the complexes, X=ONO_2 complex gave easily cis-[Ru(NO_2)(CH_3CN)(bpy)_2^+. O ne possible explanation for the mechanistic process of the rare nitrosyl-to-nitro reaction was proposed.
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