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8171452 
Journal Article 
Two new cyclic thioanions: (PPh4)(2)[1,3-P2S8] and (PPh4)(2)[Si2S6Cl2]. New synthetic access routes to PPh4[PS2Cl2] and PPh4[PS2Br2] 
Gruber, H; Muller, U 
1997 
1 
Zeitschrift fuer Anorganische und Allgemeine Chemie
ISSN: 0044-2313 
JOHANN AMBROSIUS BARTH VERLAG 
HEIDELBERG 
623 
6 
957-961 
German 
WOS:A1997XD28700009 
(PPh4)2[P2S8] was obtained from tetraphenylphosphonium polysulfide and white phosphorus in acetonitrile. According to its X-ray crystal structure analysis (4229 reflexions, R = 0.079) the P2S82- ion consists of a six-membered ring in chair conformation made up from four sulfur and two phosphorus atoms in 1,3 positions; in addition, each P atom has two terminal sulfur atoms. (PPh4)2[Si2S6Cl 2]·2 CH2Cl2 was obtained from Na2S4, PPh4Cl and SiCl4 in dichloromethane. The Si2S6Cl22- ion also has a six-membered ring structure, consisting of four sulfur and two silicon atoms in 1,4 positions (X-ray structure analysis, 2694 reflexions, R = 0.032). PPh4[PS2Cl2] is accessible by the following reactions: 1. P4S3 + PPh4Cl + chlorine in CH2Cl2; 2. PSCl3 + Na2S4 + PPh4Cl in CH2Cl2; 3. PCl5 + Na2S4 + PPh4Cl in acetonitrile; 4. PCl3 + Na2S4 + PPh4Cl in acetonitrile; 5. P4S10 + Na2S4 + PPh4Cl in acetonitrile. P4S3 or P4S10 react with PPh4Cl and bromine to yield PPh4[PS2Br2]. PPh4[PS2Cl2] crystallizes isotypic to PPh4[PS2Br2] in the BiPh4[ClO4] structure type with orientational disorder of the PS2Cl2- ions in positions with site symmetry 4. 
cyclic thiophosphate; cyclic thiochlorosilicate; dichlorodithiophosphate; dibromodithiophosphate; crystal structures