Stereochemical Dependences of 31P-13C Spin-Spin Coupling Constants of Heterocyclic Phosphines

Yuriy Y Rusakov; Irina L Rusakova; Sergei V Fedorov; George A Gray; Leonid B Krivdin

doi:10.1021/acs.jpca.9b05385

Stereochemical Dependences of ³¹P-¹³C Spin-Spin Coupling Constants of Heterocyclic Phosphines

J Phys Chem A. 2019 Jul 25;123(29):6298-6303. doi: 10.1021/acs.jpca.9b05385. Epub 2019 Jul 11.

Authors

Yuriy Y Rusakov¹, Irina L Rusakova¹, Sergei V Fedorov¹, George A Gray², Leonid B Krivdin¹

Affiliations

¹ A. E. Favorsky Irkutsk Institute of Chemistry , Siberian Branch of the Russian Academy of Sciences , Favorsky St. 1 , 664033 Irkutsk , Russian Federation.
² Agilent Technologies , 5301 Stevens Creek Blvd , Santa Clara , California 95051 , United States.

PMID: 31260305
DOI: 10.1021/acs.jpca.9b05385

Abstract

Phosphorus-carbon spin-spin coupling constants in a series of salient heterocyclic phosphines were calculated at the SOPPA(MP2) level including evaluation of relativistic and solvent effects. A number of the locally dense basis set schemes were thoroughly investigated in terms of their accuracy versus computational demands. The most effective computational scheme was tested in a benchmark series to provide a very good correlation between ²J_PC calculated at the SOPPA(MP2) level and experiment. A marked dihedral angle dependence of ²J_PC was demonstrated, and this could be used in stereochemical studies of a wide series of organophosphorus compounds based on the phosphorus-carbon coupling constants.