Benzyl cobaloximes with thiodioximes: Synthesis, structure and reactivity

Inorganic and organometallic cobaloximes with dioxime containing Se side chain: Synthesis, characterization and comparison with related B12 model compounds

“…Complexes 1 and 2 have a symmetry plane, and the molecular building blocks are formed by a symmetric operation on one asymmetric unit. The benzyl group in complexes 6 and 7 is located over the dioxime wing and shows some interaction with the dioxime ring current similar to the reported benzyl cobaloximes [31,32].…”

“…A significant reactivity difference in oxygen insertion in 6 and 7 has been observed, although the CoÀC bond length is similar in both cases. Recently we have proposed that the puckering in the Co(dioxime) 2 (a and d values) influences the CoÀC bond reactivity [32]. This may be the case here also; the d values are similar but a values are different and changes from negative to positive in complexes 6 and 7, respectively.…”

Pyrazine bridged dicobaloximes with bis(thiophenyl)glyoxime and their molecular oxygen insertion

“…dmgH > gH [26,32e36]. Furthermore, we have also seen the puckering of the Co(dioxime) 2 unit, caused by the strategic variation of dioxime chain, the eSR substituent significantly influences the CoeC bond reactivity [27]. However molecular oxygen insertion in dicobaloximes has never been studied.…”

“…We have also seen how the competition between steric and p interaction between axial benzyl group and equatorial dioxime ligand dictates the conformation of two cobaloxime units. Our recent work on mono organocobaloximes with thiodioximes has shown how the eSR substituent affects the structure, spectroscopy and most importantly the CoeC bond reactivity [26,27]. Here we have extended the study to dicobaloximes.…”