THE PREPARATION AND X-RAY STRUCTURE OF [ASPH(4)][PH(2)P(S)NSIME(3)]CENTER-DOT-O.5THF

The reaction of Ph(2)P(S)N(SiMe(3))(2) with potassium tert-butoxide in a 1:1 molar ratio produces K[Ph(2)P(S)NSiMe(3)], which was converted to the AsPh(4)(+) salt by metathesis with [AsPh(4)]Cl. The X-ray crystal structure of [AsPh(4)][Ph(2)P(S)NSiMe(3) . 0.5 THF consists of noninteracting AsPh(4)(+) and Ph(2)P(S)NSiMe(3)(-) ions with d(P-S) = 1.980(4) Angstrom and d(P-N) = 1.555(8) Angstrom. The PNSi bite angle in the anion is 136.3(5)degrees. Electrophilic attack by Ph(2)P(S)Cl occurs at the sulfur atom of Ph(2)P(S)NSiMe(3)(-). The oxidation of the anion with iodine produces a disulfide which regenerates K[Ph(2)P(S)NSiMe(2)] upon treatment with potassium tert-butoxide.