LAUSR

Abstract The reductive coupling and hydrogenation of alkenes were catalyzed by the B12 model complex, heptamethyl cobyrinate perchlorate (1), in the presence of acid during electrolysis at −0.7 V vs. Ag/AgCl in acetonitrile. Conjugated alkenes showed a good reactivity during electrolysis to form reduced products. The product distributions were dependent on the substituents at the C C bond of the alkenes. ESR spin-trapping experiments using 5,5-dimethylpyrroline N-oxide (DMPO) revealed that the cobalt-hydrogen complex (Co H complex) should be formed during the electrolysis and it functioned as an intermediate for the alkene reduction. The electrolysis was also applied to an alkyne, such as phenylacetylene, to form 2,3-diphenylbutane (racemic and meso) and ethylbenzene via styrene as reductive coupling and hydrogenated products, respectively.