Ligand field splitting in homoleptic tetrahedral d(10) transition metal complexes. Spectrochemical series

摘要

The ligand field splitting At in a number of homoleptic tetrahedral complexes of Cu(I) and Ni(O) are determined from electronic structure calculations by OFT at the BP86/6-31+G(d,p) and BP86/LanL2DZ levels. Some ligands are monodentate (e.g. CO, NH3, CI- etc.) and some are bidentate (e.g. ethylenediamine, 2,2'-bipyridine etc.). The At values obtained with the two basis sets for a given metal ion are comparable except for the phosphines. They correlate linearly with Shimura's d(Co) parameters which are considered to be most effective for constructing a spectrochemical series. Earlier it was believed that the do, parameters are applicable only to the octahedral complexes of cobalt(III). It is further shown that the d(Co) parameters bear a linear relationship with Chatt's ligand constants P-L. Implications are discussed. (C) 2018 Elsevier B.V. All rights reserved.