DFT study of the systematic variations in metal-ligand bond lengths of coordination complexes: the crucial role of the condensed phase.
The experimental M-A and M-B distances in several series of [MAnBm-n]-type complexes have been studied by DFT. Many of the structural features of the series, such as trans influences and sterically induced bond elongations, are not reproduced correctly in gas-phase DFT calculations. However, the correct trends are recovered by explicitly including environmental effects via the COSMO solvation model. These observations imply that the condensed-phase environment plays a critical role in determining the geometric structure of coordination complexes. Thus, any apparently satisfactory reproduction of the condensed-phase structure by an in vacuo calculation may mask an incorrect treatment of the interplay between different ligands attached to the same metal center.
Hocking
Rosalie K
RK
CHMR, School of Chemistry, The University of Sydney, 2006, Australia, Department of Chemistry, University of Warwick, Coventry, UK. rosalie.hocking@csiro.au
Deeth
Robert J
RJ
Hambley
Trevor W
TW