DFT Calculations of 31P NMR Chemical Shifts of σ-Donor Phosphorus Atoms in Platinum Complexes

Abstract

The scopes and limitations of available computational approaches for evaluating ³¹P NMR chemical shifts of σ-donor phosphorus atoms in platinum complexes were analyzed. It was shown that satisfactory accuracy can be achieved only when shielding is calculated within a fully relativistic formalism (mDKS). Geometry optimization at the PBE0/{6-31+G(d); Pt(SDD)} level was found to be optimal in terms of cost-to-accuracy ratio. The effectiveness of the proposed approach was demonstrated for the analysis of cis/trans isomerism in platinum complexes.