Conformational analysis and stereochemical dependences of (31)P-(1)H spin-spin coupling constants of bis(2-phenethyl)vinylphosphine and related phosphine chalcogenides.

Theoretical energy-based conformational analysis of bis(2-phenethyl)vinylphosphine and related phosphine oxide, sulfide and selenide synthesized from available secondary phosphine chalcogenides and vinyl sulfoxides is performed at the MP2/6-311G** level to study stereochemical behavior of their (31)P-(1)H spin-spin coupling constants measured experimentally and calculated at different levels of theory. All four title compounds are shown to exist in the equilibrium mixture of two conformers: major planar s-cis and minor orthogonal ones, while (31)P-(1) H spin-spin coupling constants under study are found to demonstrate marked stereochemical dependences with respect to the geometry of the coupling pathways, and to the internal rotation of the vinyl group around the P(X)-C bonds (X = LP, O, S and Se), opening a new guide in the conformational studies of unsaturated phosphines and phosphine chalcogenides.