189556-95-4Relevant articles and documents
Transfer of Sulfur from Arsenic and Antimony Sulfides to Phosphorus Sulfides. Rational Syntheses of Several Less-Common P4Sn Species
Jason, Mark E.
, p. 2641 - 2646 (2008/10/09)
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.
Multiphase characterization of phosphorus sulfides by multidimensional and MAS-31P NMR spectroscopy. Molecular transformations and exchange pathways at high temperatures
Bjorholm,Jakobsen
, p. 27 - 32 (2007/10/02)
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.
