The electrochemical reduction of benzyl and 4-(trifluoromethyl)benzyl chlorides catalyzed by Co(salen) (H2salen = N,N’-bis(salicylidene)-ethane-1,2-diamine was studied in acetonitrile. Electrogenerated Co(I)(salen) reacts with the halide to give an organocobalt(III) complex. Further one-electron reduction of the latter yields an unstable intermediate that undergoes rapid decomposition by cleavage of the Co-C bond. The mechanism of bond breaking in the one-electron-reduced organocobalt(II) complex was investigated. The results of preparative electrolysis on solutions containing Co(salen) and benzyl chloride, performed under different experimental conditions, in particular in the presence of radical or carbanion scavengers, indicate hemolytic cleavage of the Co-C bond.
Mechanism of the electrochemical reduction of benzyl chlorides catalysed by Co(salen)
AHMED ISSE, ABDIRISAK;GENNARO, ARMANDO;VIANELLO, ELIO
1998
Abstract
The electrochemical reduction of benzyl and 4-(trifluoromethyl)benzyl chlorides catalyzed by Co(salen) (H2salen = N,N’-bis(salicylidene)-ethane-1,2-diamine was studied in acetonitrile. Electrogenerated Co(I)(salen) reacts with the halide to give an organocobalt(III) complex. Further one-electron reduction of the latter yields an unstable intermediate that undergoes rapid decomposition by cleavage of the Co-C bond. The mechanism of bond breaking in the one-electron-reduced organocobalt(II) complex was investigated. The results of preparative electrolysis on solutions containing Co(salen) and benzyl chloride, performed under different experimental conditions, in particular in the presence of radical or carbanion scavengers, indicate hemolytic cleavage of the Co-C bond.
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