Electric and Magnetic Anisotropy in Structural Organophosphorus Chemistry

Abstract

Abstract The principles of study of the electric polarizability and magnetic susceptibility anisotropy of phosphorus derivatives have been discussed. The molar constants of birefringence in the transverse magnetic field (Cotton-frlouton constants, lo18 e.m.u.) have been determined for 2-methoxy-4-methyl-1,3,2-dioxaphosphorinane (-1.31, its 2-oxoanalogue (1.5), 2-thioanalogue (-16.3), phosphorus chloride (-112), phosphorus oxychloride (-87), and thiophosphoryl chloride (-12). The principal semiaxes of molecular magnetic susceptibility ellipsoids (1029 cm3) for the three latter compounds have been found equal: PCl3 k1 −9.90, k 2,3 −11.36; POCl3 kl −8.83, k 2,3 −11.28; PSCl3 k1 −13.28, k2,3, −13.17. The components of the magnetic susceptibility tensors of the phosphorus lone pair kL −2.15, kt −2.32 and of the bonds P-0 kL −4.35, kT −2.23; P-Cl kL −4.17, kT −2.05; P→O kL −1.11, kT −0.44; P→S kL −4.17, kT −2.17 have been calculated using data on the magnetic anisotropy effects on chemical shifts in PYR spectra of dioxaphosphorinanes. The relationship between the mean values of the magnetic susceptibility and electric polarizability phosphorus derivatives has been established, k = −0.060–1.046.10−5 b. The magnetic anisotropies of bonds have been shown to depend on their environment, for phosphoryl on the Kabachnik constants of substituents at the phosphorus atom.