Relativistic heavy atom effect on the 31 P NMR parameters of phosphine chalcogenides. Part 1. Chemical shifts.

Four-component density functional theory calculations of 31 P NMR chemical shifts have been performed for the representative series of 56 phosphine chalcogenides in order to investigate an influence of different functional groups on the heavy atom relativistic effect on the NMR chemical shifts of light phosphorous atoms (Heavy Atom on Light Atom effect). The validity of the 4-component density functional theory approach used for the wide-scale calculations of the phosphorous chemical shifts in a wide series of phosphine chalcogenides has been confirmed on a small series of 5 representative compounds with the aid of high-quality coupled cluster singles and doubles calculations taking into account solvent, vibrational, and the relativistic corrections in comparison with the experiment.