Zwei neue cyclische Thioanionen: (PPh4)2[1,3-P2S8] und (PPh4)2[Si2S6Cl2]. Neue Synthesewege zu PPh4[PS2Cl2] und PPh4[PS2Br2]

(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)[Si2S6Cl2]. 2CH(2)Cl(2) 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) over bar.