- Transfer of Sulfur from Arsenic and Antimony Sulfides to Phosphorus Sulfides. Rational Syntheses of Several Less-Common P4Sn Species
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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.
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p. 2641 - 2646
(2008/10/09)
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- Products and Mechanisms in the Oxidation of Phosphorus by Sulfur at Low Temperature
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The oxidation of phosphorus by sulfur at low temperatures (8 diradical. This proposal is supported by the observed rate at which the sulfldes are formed and the distribution of the sulfide product stoichiometries. Photoinitiation of this oxidation at 0 °C produces a similar array of sulfldes. The differences in the product distributions between the thermal and photochemical processes facilitate the understanding of the mother-daughter relationships between the products. The effects of oxidation by sulfur and reduction by phosphorus have been determined for several of the known phosphorus sulfides. The characterizations of phosphorus compounds in molten mixtures of phosphorus and sulfur were performed by 31P NMR and Raman spectroscopy directly on the reaction mixtures.
- Jason, Mark E.,Ngo, Toan,Rahman, Shahidur
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p. 2633 - 2640
(2008/10/09)
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- The Molecular Composition of Solidified Phosphorus-Sulfur Melts and the Crystal Structure of β-P4S6
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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.
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- Infrared spectra of P4S10 and its decomposition products in solid argon
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The vapor from solid molecular P4S10 in a stainless steel Knudsen cell at 175°C was trapped in solid argon for infrared spectroscopic study. Comparison with infrared spectra of solid P4S10 and P4S9 provides a basis for identification of molecular P4S10 and P4S9, which were isolated in comparable yields. A similar fraction of product absorptions is identified as phosphorus sulfides (PS, PS2) and diphosphorus sulfides (P2S4, P2S5), with P2S5 being the major diphosphorus species in the equilibrium vapor and in superheated vapor. Photolysis of P4S10 and O3 mixtures produced new infrared absorptions for SO2 and the terminal oxide P4S9O.
- Andrews, Lester,Reynolds, Gregg G.,Mielke, Zofia,McCluskey, Matthew
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p. 5222 - 5225
(2008/10/08)
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- On the Reactions of Hexamethyldistannoxane and Hexamethyldistannthiane with Phosphorus-oxy and -thio-halides. Vibrational Spectra of (Me2PS)2O and (Me2PS)2S
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Me3SnO2PCl2 and (Me2PS)2O are prepared from the reactions of (Me3Sn)2O with POCl3 (1:1) and with Me2PSCl (1:2), respectively.The reactions of (Me3Sn)2S with Me2PSCl and with PSBr3 lead to the formation of (Me2PS)2S and P4S9, respectively.POCl3 reacts with (Me3Sn)2S to give unidentified products as a result of O/S exchange.The i.r. and Raman spectra of the solids (Me2PS)2O and (Me2PS)2S and the Raman spectra of the molten compounds are reported and the frequencies assigned. - Key words: Reactions, Preparations, Vibrational Spectra
- Shihada, Abdel-Fattah,Jasim, Ihsan A. M.
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p. 783 - 787
(2007/10/02)
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- N.M.R. Evidence for the Existence of P4S8
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N.m.r. evidence indicates that the primary product of the desulphuration of P4S9 by Ph3P is P4S8, a new species of limited stability.
- Barieux, Jean-Jacques,Demarcq, Michel C.
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p. 176 - 177
(2007/10/02)
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- 31P-KERNRESENANZUNTERSUCHUNGEN VON P4S9 UND P4S10
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The preparation of P4S9 from P4S3 and sulfur in decalin is described.The 31P nmr spectra of P4S9 and P4S10 are presented and discussed.
- Thamm, R.,Heckmann, G.,Fluck, E.
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p. 319 - 324
(2007/10/02)
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