SOLID-STATE P-31 NMR AND X-RAY CRYSTALLOGRAPHIC STUDIES OF TERTIARY PHOSPHINES AND THEIR DERIVATIVES

High-resolution, solid-state P-31 NMR spectra of PPh3 and its oxide, sulfide, and selenide are presented and interpreted in terms of reported space group information from X-ray crystallographic studies. The spectra of Ph2PCH2CH2PPh2 and Ph2PCH2PPh2 are similarly described. In order to fully interpret the NMR spectra, the X-ray crystal structures of PCy3 (1), OPCy3 (2), and SePCy3 (3) were determined. Data are as follows: 1, fw = 280.44, trigonal, P3(1), a = 9.893 (2) angstrom, c = 15.446 (3) angstrom, V = 1309.2 angstrom 3, Z = 3, D(x) = 1.07 g cm-3, lambda(Mo K-alpha-1) = 0.70930 angstrom, mu = 1.4 cm-1, F(000) = 468, T = 294 (1) K, R = 0.045 for 1092 unique reflections with F2 > 3-sigma(F2); 2, fw = 296.44, triclinic, P1BAR, a = 9.799 (4) angstrom, b = 16.402 (6) angstrom, c = 17.067 (6) angstrom, alpha = 101.30 (3)-degrees, beta = 90.39 (3)-degrees, gamma = 99.86 (3)-degrees, V = 2647.8 angstrom 3, Z = 6, D(x) = 1.23 g cm-3, lambda(Mo K-alphaBAR) = 0.71073 angstrom, mu = 1.6 cm-1, F(000) = 1086, T = 294 (1) K, R = 0.051 for 4939 unique reflections with F2 > 3-sigma(F2); 3, fw = 359.40, orthorhombic, Pnma, a = 11.110 (1) angstrom, b = 15.803 (2) angstrom, V = 1819.6 angstrom 3, Z = 4, D(x) = 1.31 g cm-3, lambda(Mo K-alpha-BAR) = 0.71073 angstrom, mu = 21.2 cm-1, F(000) = 760, T = 294 (1) K, R = 0.034 for 1308 unique reflections with F2 > 3-sigma(F2).