Inorganic Chemistry, Vol.35, No.10, 2915-2929, 1996
Fluoride-Ion Induced Reactions of Silicon-Oxygen and Silicon-Sulfur Bonds with Hexafluorocyclotriphosphazenes - Synthesis, Reactivity, and X-Ray Structural-Analyses of Sulfur/Oxygen-Containing Monospirofluorophosphazenes
Bifunctional trimethylsilyl ethers/thioethers/dithioethers react readily with N3P3F6 in the presence of a catalytic amount of CsF in THF to yield spirofluorophosphazenes or dangling or bridged fluorophosphazenes with concomitant elimination of Me(3)SiF. With sulfur-containing aliphatic bifunctional reagents of the type Me(3)SiX(CH2)(n)SSiMe(3), five- and six-membered monospirofluorophosphazenes, N3P3F4[X(CH2)(m)S] [X = 0 or S; n = 2 or 3] (1-4), are formed in good yield. Crystals of N3P3F4[OCH2CH2S] (1) are monoclinic, P2(1)/c; fw = 287.05, a = 8.727(10) Angstrom, b = 11.246(2) Angstrom, c = 9.787(2) Angstrom, beta = 100.91(10)degrees, V = 943.2(3) Angstrom(3) and Z = 4. N3P3P4[OCH2CH2CH2S] (2) is orthorhombic, Pbca; fw = 301.08, a = 12.399(4) Angstrom, b = 10.105(2) Angstrom, c = 16.787(2) Angstrom, V = 2103.3(9) Angstrom(3), Z = 8. N3P3F4[SCH2CH2S] (3) is triclinic, ; fw = 303.11, a = 9.501(2) Angstrom, b = 9.764(3) Angstrom, c = 11.092(5) Angstrom, alpha = 74.97 degrees, beta = 88.03 degrees, gamma = 85.85 degrees, V = 991.0(6) Angstrom(3), and Z = 2. N3P3F4[SCH2CH2CH2S] (4) is orthorhombic, Fdd2; fw = 317.14, a = 18.238(4) Angstrom, b = 41.390(8) Angstrom, c = 5.965(12) Angstrom, V = 4503(2) Angstrom(3), and Z = 16. The P-31 NMR spectra of these empt is made to explain this observation on the basis of structural parameters. Reactions of N3P3F6 With disiloxanes such as (Me(3)SiOCH(2)CH(2))(2)O at temperatures below 80 degrees C yield only the dangling product 5a.