- Transfer of Sulfur from Arsenic and Antimony Sulfides to Phosphorus Sulfides. Rational Syntheses of Several Less-Common P4Sn Species
-
It has been shown that triphenylarsenic sulfide and triphenylantimony sulfide rapidly transfer sulfur to a number of the known phosphorus sulfides. The reactions are performed at or below room temperature in carbon disulfide solutions. The transfers are neither highly selective nor random, making them useful but not ideal for synthetic purposes. The moderate selectivities of the reactions have been used in the assignment of structures to two new phosphorus sulfides, structures with molecular formulas P4S6 and P4S8. The reactions of P4S3 are unusual in that products with 7-9 sulfur atoms in the molecule are formed competitively with low sulfur products. The usefulness of triphenylantimony sulfide is limited by its tendency to undergo reductive elimination of sulfur. This reduction takes the form of a disproportionation to give triphenylantimony and elemental sulfur and has been shown to occur by a second-order process that appears to involve the formation of disulfur, S2.
- Jason, Mark E.
-
p. 2641 - 2646
(2008/10/09)
-
- The Molecular Composition of Solidified Phosphorus-Sulfur Melts and the Crystal Structure of β-P4S6
-
Phosphorus sulfur melts were annealed for one week at 673 K and then quenched in ice water. The solids were dissolved in CS2 and the concentrations of phosphorus sulfides were determined by (31)P NMR spectroscopy. Samples containing between 44 ant 70 mol% sulfur dissolved completely in CS2. Between 0 and 42 mol% remains an insoluble residue of red phosphorus. Above 72 mol% it consisted of sulfur chains linked by phosphorus atoms. The solutions contained mainly the congruently melting compounds P4S3,P4S7, and P4S10 having maximum concentrations at their stoichiometric c ompositions. Other compounds P4Sn (n=4-9) which decompose on heating, according to the phase diagram, were also found in surprisingly high concentrations. One of these was β-P4S6 which crystallizes in the monoclinic space group P21/C with the lattice parameters a=702.4(2), b=1205.6(2), c=1148.9(6) pm, and β=103.4(2)° Reaction of white phosphorus with sulfur was also investigated. In contrast to the results of previous authors, who described the system P4-S8 below 373 K as eutectic,we found that the elements reacted below this temperature.
- Blachnik, Roger,Peukert, Ulrike,Czediwoda, Anette,Engelen, B.,Boldt, K.
-
-