The Preparation and X‐Ray Structure of [AsPh 4 ][Ph 2 P(S)NSiMe 3 ] · 0.5 THF

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(PS) = 1.980(4) Å and d(PN) = 1.555(8) Å. The PNSi bite angle in the anion is 136.3(5)°. 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.