Bimolecular homolytic reactions of alkylcobalt complexes

The reactions of RCoL1(H2O)(2+) (R = CH3, C2H5 and n-C3H7; L-1 = 5,7,7,12,14,14-hexamethyl-1,4,8,1 1-tetraazacyclotetradeca-4,1 I diene) and CH3CoL2 (H2O)(2+) (L-2 = 1,4,8,11 -tetraazacyclotetradecane) with Cr2+ in aqueous solution were studied. The reaction products were CoL1 (H2O)(2+)(2) (or CoL2 (H2O)(2+)(2)) and RCr2+ following which the related alkanes were obtained via acidolysis. The reaction mechanism appears to consist of an SH2 displacement at the saturated carbon. The reactivity is clearly dependent on the size of the alkyl group, the ligand and the configuration of the complex. The kinetics for this reaction were also studied at various temperatures. The reaction of RCoL1(H2O)(2+) with V2+ was investigated as well in this study. (C) 2007 Elsevier Ltd. All rights reserved.