131105-01-6

Upstream product

• 7704-34-9 sulfur 
• 7783-06-4 hydrogen sulfide 
• 7719-12-2 phosphorus trichloride 
• 1314-85-8 phosphorus sulfide 
• 10544-50-0 sulfur 
• 12185-10-3 phosphorus 
• 15578-54-8 tetraphosphorus pentasulphide 
• 20419-10-7 β-P4S5 
• 3937-40-4 triphenyl arsine sulfide 
• 20419-10-7 P4S5, β 

Downstream Products

• 12037-82-0 phosphorus sulfide 

Relevant academic research and scientific papers

A solid state 31P NMR study of the synthesis of phosphorus sulfides from PCI3 and H2S in microporous materials

The interaction and reaction of PCl3 and PCl3-H2S mixtures with the microporous materials Silicalite, ALPO-5, NaY, NaX, and NaA have been investigated, with the intention of producing phosphorus sulfide clusters in the pores. A rich chemistry was observed and monitored by solid state 31P NMR. The presence of P4S3, α-P4S5, β-P4S6, and P4S7 inside the NaY α-cages was demonstrated, as well as a new species that is possibly a third geometric isomer of P4S4 with C(3v) symmetry. 129Xe NMR showed the exclusion of Xe from the micropores by the phosphorus sulfides. Sulfides lower than P4S7 are small enough that they undergo rapid pseudo-isotropic reorientation inside the NaY α-cage.

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.

Products and Mechanisms in the Oxidation of Phosphorus by Sulfur at Low Temperature

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.

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.

Multiphase characterization of phosphorus sulfides by multidimensional and MAS-31P NMR spectroscopy. Molecular transformations and exchange pathways at high temperatures

High-temperature 1D and 2D exchange 31P-NMR spectra of melts of pure and well-defined phosphorus sulfides show that, e.g., β-P4S5 or mixtures of P4S3 and sulfur transform into mixtures of at least eight different P4Sn (n = 3-7) species which are identified and quantified. Transformations and exchange pathways between the different P4Sn species in the melts are revealed by the 2D exchange 31P-NMR spectra at 225-250 °C. Furthermore, the exchange correlations observed from these spectra yield unambiguous assignments of the unknown or earlier incorrectly assigned 31P chemical shifts for β-P4S6, β-P4S5, α-P4S5, and a new P4S6 isomer (α-P4S6). These assignments are extremely valuable for a correct interpretation of the complex solid-state magic angle spinning (MAS)-NMR spectra of phosphorus sulfides. Two polymorphs for both β-P4S5 and α-P4S6 (the predominant species in the β-P4S5 melt and isolated here for the first time) have been isolated and characterized by high-speed 31P MAS-NMR spectroscopy. Molecular distortions, caused by crystal packing and not easily detected by XRD, are observed for all four polymorphs. These distortions cause nonequivalence between phosphorus atoms which are equivalent for the free molecules. Thereby otherwise unobservable isotropic 1J(P,P)'s have been determined from solid-state NMR spectroscopy.