Inorganic cobaloximes with mixed dioxime equatorial ligands: a convenient one pot synthesis and cis influence studies: X-ray crystal structures of N3CoIII(dmgH)(dpgH)Py and N3CoIII(chgH)(dpgH)Py

A simple and general route to the synthesis of cobaloxime with mixed dioxime ligands, XCo(L)(L′)Py, L,L′=dmgH/dpgH and chgH/dpgH; X=Cl, Br, NO2, N3, has been described. These compounds are reported for the first time. The synthesis is confirmed by the X-ray structures of N3Co(dmgH)(dpgH)Py and N3Co(chgH)(dpgH)Py. The cis and trans effects on these complexes and on XCo(L)2Py (L=dmgH, chgH, dpgH; X=Cl, Br, NO2, N3) complexes have been studied by 1H-, 13C-NMR, UV, and X-ray. For a range of X ligands, a clear trend between the 1H, 13C chemical shifts of the equatorial and axial ligands as well as with the Co–dioxime CT band has been observed. The analysis of the 13C values and X-ray data shows that one dioxime wing effects the other dioxime wing in the mixed dioxime complexes.