Structural Analysis and Reactivity of Tetramethylcopper(III) Complex towards Nitrogen Donor Ligands by Density Functional Theory

DFT studies are carried out on some ligand substitution reactions of tetramethylcuprate(III) (TMC) complex with five different nitrogen donor ligands as probe ligands. The geometry optimization of the possible nine model systems and the frequency calculations are carried out at DFT level using LANL2DZ basis set. The selected structural parameters of optimized model systems of Cu(III) complexes are reported and discussed. The change in the M-C bond distance in TMC due to substitution by probe ligands is explained. Natural population analysis (NPA) has been carried out for these complexes to establish the charge of copper in these complexes. A detailed population analysis of valence orbitals of copper complexes supports the existence of d8 configuration for metal in complexes and there is evidence for the transmission of electrons from the nitrogen donor atom to dxy, dx2-y2, and 4s orbitals. Bond order calculations have been performed for all the complexes to probe the interaction between Cu(III) and the ligand. The stability of the complexes is ascertained from the computed chemical hardness. In order to understand the nature of Cu(III)-L (L = N donors) and Cu(III)-Me bonds in different complexes, Energy Decomposition Analysis (EDA) has been carried out for all the complexes chosen in the theoretical study. Thermodynamic feasibility of these reactions is investigated in terms of free energy changes of these reactions