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The Preparation and X‐Ray Structure of [AsPh 4 ][Ph 2 P(S)NSiMe 3 ] · 0.5 THF
Author(s) -
Chivers Tristram,
Parvez Massod,
Seay Michelle A.
Publication year - 1995
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.19956211102
Subject(s) - chemistry , potassium , molar ratio , electrophile , iodine , ion , catalysis , medicinal chemistry , organic chemistry
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.