Benzyl cobaloximes with thiodioximes: Synthesis, structure and reactivity

Five benzyl cobaloximes with different thiodioximes, BnCo[d(SR)gH]₂Py, have been synthesized and four of these complexes have been characterized by X-ray. The reactivity of these complexes towards molecular oxygen has been studied. The puckering of the Co(dioxime)₂ unit, caused by dioxime side chain, the SR group, significantly influences the Co-C bond reactivity. Structural features in one of the oxygen inserted cobaloximes have been studied to confirm if puckering of dioxime is the guiding factor. The reactivity is also affected, to some extent, by the C-H…π interaction between the benzyl and the dioxime moiety.