Computational study of the [(CO)2(benzoate)MII/III(terephthalate)]0/1+ complexes with M = V, Cr, Mn, Fe and Co

Abstract

Computational study at DFT-B3LYP/LANL2DZ level of theory is carried out to evaluate structural, bonding and energetic characteristics of cis/trans isomers of the [(CO)2(benzoate)MII/III(terephthalate)]0/1+ complexes with 3d transition metals M = V, Cr, Mn, Fe and Co. Results of this study show that all cis/trans isomers of these complexes in their two oxidation states are stable with distinctly different structures. As a general trend, for all cis/trans isomers of these complexes, the MO(benzoate) and MO(terephthalate) bonds are shorter for the MIII oxidation state of the metal ion compared to those for the corresponding MII oxidation state. Also, structure of the set of four MO bonds are almost asymmetric such that the optimized MII/IIIO (terephthalate) bond lengths are slightly longer than the MII/IIIO(benzoate) bond lengths. The coordination MO bonds structure of the cis/trans isomers of the [(CO)2(benzoate)CoII(terephthalate)] complex have the most asymmetries, and interestingly, its trans isomer is more asymmetric than its cis isomer. The MIII complexes have larger electric dipole moments compared to their corresponding MII complexes. Furthermore, cis/trans isomerization has no significant effect on the size of electric dipole moment for the MII complexes.