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Trivinylphosphine and trivinylphosphine chalcogenides: stereochemical trends of 31P1H spin–spin coupling constants

✍ Scribed by Sergey V. Fedorov; Leonid B. Krivdin; Yury Yu. Rusakov; Nataliya A. Chernysheva; Valentina L. Mikhailenko

Publisher
John Wiley and Sons
Year
2010
Tongue
English
Weight
331 KB
Volume
48
Category
Article
ISSN
0749-1581

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✦ Synopsis

A combined theoretical and experimental study of the stereochemical behavior of (31)P-(1)H spin-spin coupling constants has been performed in the series of trivinylphosphine and related trivinylphosphine oxide, sulfide and selenide. Theoretical energy-based conformational analysis of the title compounds performed at the MP2/6-311G** level reveals that each of the four compounds of this series exists in the equilibrium mixture of five true-minimum conformers, namely s-cis-s-cis-s-cis, s-cis-s-cis-gauche, syn-s-cis-gauche-gauche, anti-s-cis-gauche-gauche and gauche-gauche-gauche, which were taken into account in the conformational averaging of (31)P-(1)H spin-spin couplings calculated at the second-order polarization propagator approach/aug-cc-pVTZ-J level of theory. All (31)P-(1)H spin-spin coupling constants involving phosphorus and either of the vinyl protons are found to demonstrate a marked stereochemical dependences with respect to the geometry of the coupling pathway and internal rotation of the vinyl group around the P-C bond which is of major importance in the stereochemical studies of the unsaturated phosphines and phosphine chalcogenides.

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