The thermal decompositions of alkyl cobaloximes: a correction to the literature

Mass spectrometric studies have clarified the stages of thermal decomposition of alkyl cobaloximes. For the thermolysis of complexes containing pyridine as the base ligand and primary and secondary alkyl as the top axial ligand, all examples examined lose the top axial alkyl ligand first, followed by pyridine, sometimes at a significantly higher temperature. For examples with water as base ligand, primary alkyl compounds lose water first, but in the cases of secondary alkyl complexes, the hydrocarbon group leaves at the lower temperature. In the final stage of thermal disruption, equatorial ligands such as dimethylglyoxime and cyclohexane-1,2-dione dioxime undergo symmetrical cleavage and dehydration to form the corresponding nitriles, acetonitrile and hexanedinitrile.