Electron Density Redistribution in the System GeCl4←O=C[N(CH3)2]2 upon Coordination Bond Formation

Abstract

Quantum-chemical calculations of the system Cl₄Ge←O=C[N(CH₃)₂]₂ with full geometry optimization were performed by RHF/6-31G(d) and MP2/6-31G(d) methods. The calculations took into account that the Ge–Cl axial bond and the O=C bond are not at one line, as opposed to the previous belief. The MP2/6-31G(d) calculations of this system were also performed for various distances between coordination centers, and for GeCl₄ and O=C[N(CH₃)₂]₂ molecules, with full geometry optimization. The results of the calculations were used to quantify electron density redistribution in the system upon coordination bond formation. The electron density of chlorine atoms, especially, of the axial chlorine atom, was shown to increase upon coordination bond formation due to its transfer from the ligand hydrogen atoms and Ge–Cl bond polarization. The partial negative charge of the oxygen atom and the positive charge of the carbonyl carbon atom increase in association.