Bonding Properties Related with Chiral Discrimination in Dinuclear Metal Complexes of Group 10

摘要: A series of neutral dinuclear homo- and heterochiral complexes formed by hydrazine (a molecule with axial chirality), a metal atom group 10 (Ni, Pd, Pt), halogen atoms (F, Cl, Br, I) was studied computational methods including density functional theory. In the optimized structures were always found to be energetically favored. The chiral discrimination depends on contributions coming from anions attached them. Moreover, relative energies are correlated electronegativity metals halogens as well distances bond critical points in metal–nitrogen bonds. Also smaller deviation ligand–metal–ligand angles ideal value 90° corresponds complexes. An analysis bonding properties reveals complex mechanism for behavior electron lone pairs nitrogen atoms. electronic NBO (Natural Bond Orbital) QTAIM (Quantum Theory Atoms Molecules) methods. energy differences between stabilizing related interactions an pair coordinated opposite M–X antibonding orbital explain total diastereomeric homochiral have systematically more negative values complexes; this can interpreteted measure trans influence. Small cis influence mainly nickel M–N bonds polar higher order than that ones, shown (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)