The results of MWG calculations of the electronic structures of real Co(III) complexes [Co(HD)2L1L2] n were used to analyze the electron density distribution and to determine the charges on atoms and configurations, where nis the charge of the complex and HD is the acid residue of dimethylglyoxime (H2D); L1= NH3at L2= NH3, Cl–, Br–, or I–and L1= L2= Cl–; and L1= H2O or NO– 2at L2= NO– 2, with self-consistency over all atoms of the system and over d, s, and pconfigurations of cobalt. The mutual influence of the ligands (trans- and cis-) was shown to be determined by the atomic charges and bond orders on the axial coordinate and in the equatorial plane of the complex. The following order of the trans-effect was proposed: I–> Br–> Cl–> NO– 2> NH3> H2O. The effects of the electronic factors on distorsion and conformational processes in the complexes were discussed.