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 (RU(II)-NO2) TO GIVE MONOOXYGEN MOIETY (RU(IV)=O) DEPENDS ON THE AMBIENT LIGAND (X)

被引：9
|
作者：
NAGAO, N [1 ]
NAGAO, H [1 ]
NISHIMURA, H [1 ]
KURODA, H [1 ]
SATOH, K [1 ]
HOWELL, FS [1 ]
MUKAIDA, M [1 ]
机构：
[1] SOPHIA UNIV, FAC SCI & TECHNOL,DEPT CHEM,KIOI CHO 7-1, CHIYODA KU, TOKYO 102, JAPAN
来源：
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN | 1993年 / 66卷 / 05期
关键词：
D O I：
10.1246/bcsj.66.1397
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The electrochemical behavior of trans-[R-(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.
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页码：1397 / 1403
页数：7
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