Abstract
The ability of nickel(II) macrocycle and coordination complexes 1−8 to mediate the reductive dehalogenation of cyclohexyl bromide and the CH3−S bond cleavage of methyl CoM by sodium borohydride in diglyme/alcohol, DMF/alcohol, or acetonitrile/alcohol was investigated. Methyl CoM, or CH3SCH2CH2SO3-, is the cofactor that carries the methyl group in the final step of methanogenesis in methanogenic bacteria. Because of the potential for production of the heterogeneous catalyst nickel boride during these reactions, the activities of several nickel salts that afford nickel boride when reduced with borohydride were examined for purposes of comparison. Complexes 1−8 homogeneously catalyze the dehalogenation of cyclohexyl bromide by sodium borohydride. The facility of the reaction varies markedly with the structure of the ligands and the solvent composition. Nickel boride is a moderately active heterogeneous catalyst for the dehalogenation of cyclohexyl bromide and produces small yields of methane from methyl CoM ...
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