Theoretical description of copper Cu(I)/Cu(II) complexes in mixed ammine-aqua environment. DFT and ab initio quantum chemical study

This work is devoted to investigate the interactions of the Cu(I)/Cu(II) cation with variable ammonia–water ligand field by the quantum chemical approach. For that purpose, the optimization of the [Cu(NH3)m(H2O)n] 2+/+ complexes (where n varies from 0 to 4 or 6 and m + n = 4 or 6) has been performed at the DFT/6-31+G(d) level of theory in conjunction with the B3PW91 hybrid functional. Based on the results of the single-point B3LYP/6-311++G(2df,2pd) calculations, the stabilization energies were determined. The two-coordinated copper(I) complexes appeared to be the most stable compounds with the remaining water or ammonia molecules in the second solvation shell. In the case of the Cu(II) systems, four-coordinated complexes were found to be the most stable. In order to examine and explain bonding characteristics, Morokuma interaction energy decomposition (for selected Cu complexes) and Natural Population Analysis for all systems were performed. It was found that the most stable structures correlate with the highest donation effects. Therefore, more polarizable ammonia molecules exhibit higher donation than water and thus make stronger bonds to copper. This can be demonstrated by the fact that the NH3 molecule always tries to occupy the first solvation shell in mixed ammine-aqua complexes. 2004 Elsevier B.V. All rights reserved.