Correlated ab initio calculations of one‐bond 31P77Se and 31P125Te spin–spin coupling constants in a series of PSe and PTe systems accounting for relativistic effects (part 2)

Synthetic chalcogen–phosphorus chemistry permanently makes new challenges to computational Nuclear Magnetic Resonance (NMR) spectroscopy, which has proven to be a powerful tool of structural analysis of chalcogen–phosphorus compounds. This paper reports on the calculations of one‐bond 31P77Se and 31P125Te NMR spin–spin coupling constants (SSCCs) in the series of phosphine selenides and tellurides. The applicability of the combined computational approach to the one‐bond 31P77Se and 31P125Te SSCCs, incorporating the composite nonrelativistic scheme, built of high‐accuracy correlated SOPPA (CC2) and Coupled Cluster Single and Double (CCSD) methods and the Density Functional Theory (DFT) relativistic corrections (four‐component level), was examined against the experiment and another scheme based on the four‐component relativistic DFT method. A special J‐oriented basis set (acv3z‐J) for selenium and tellurium atoms, developed previously by the authors, was used throughout the NMR calculations in this work at the first time. The proposed computational methodologies (combined and ‘pure’) provided a reasonable accuracy for 31P77Se and 31P125Te SSCCs against experimental data, characterizing by the mean absolute percentage errors of about 4% and 1%, and 12% and 8% for selenium and tellurium species, respectively. The present study reports typical relativistic corrections to 77Se31P and 125Te31P SSCCs, calculated within the four‐component DFT formalism for a broad series of tertiary phosphine selenides and tellurides with different substituents at phosphorus. High‐quality quantum‐chemical calculations of 1J(77Se,31P) and 1J(125Te,31P) spin–spin coupling constants in corresponding phosphine chalcogenides were systematically performed for the first time. Typical relativistic corrections were evaluated at the four‐component density functional theory level for a wide series of tertiary phosphine selenides and tellurides.