Quantum chemical studies on the enantiomerization mechanism of several [Zn(py)3(tach)]2+ derivativesElectronic supplementary information (ESI) available. See DOI: 10.1039/c2dt31722b

• Main Authors: Puchta, Ralph, Alzoubi, Basam M, Meier, Roland, Almuhtaseb, Sabah I, Walther, Markus, van Eldik, Rudi
• Format: Journal Article
• Language: English
• Published: 06.11.2012
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c2dt31722b

The enantiomerization mechanism of the trigonal-prismatic [Zn(py) 3 (tach)] 2+ complex and several derivatives has been studied by applying DFT calculations (B3LYP/LANL2DZp). The enantiomerization pathways of [Zn(py 3 tach-X)] 2+ (X = C, Si, Ge, N, P, As, O, S and Se) start from a distorted trigonal-prismatic C 3 symmetric ground state via an ideal trigonal-prismatic C 3v structure to end up in a C 3 ′ symmetric image of the ground state. The activation energy and structural data of the complexes depend on electronic and steric factors. The activation barriers of the complexes decrease in the order [Zn(py 3 tach-Ge)] 2+ > [Zn(py 3 tach-Si)] 2+ > [Zn(py 3 tach-As)] 2+ > [Zn(py 3 tach-Se)] 2+ > [Zn(py 3 tach-P)] 2+ > [Zn(py 3 tach-S)] 2+ > [Zn(py 3 tach-C)] 2+ > [Zn(py 3 tach-N)] 2+ > [Zn(py 3 tach-O)] 2+ . The enantiomerization mechanism of a series of trigonal-prismatic Zn( ii ) complexes has been studied by DFT calculations (RB3LYP/LANL2DZp). Electronic and steric effects have a significant influence on the activation barrier and the stability of the complexes.