2011
DOI: 10.1002/anie.201103485
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Rational Syntheses and Structural Characterization of Sulfur‐Rich Phosphorus Polysulfides: α‐P2S7 and β‐P2S7

Abstract: A wide range of binary compounds is known in the system phosphorus-sulfur. They consist of discrete cage-like molecules with the composition P 4 S n (n = 3-10) except for P 14 S. [1] The cages can formally be derived from the P 4 tetrahedron of white phosphorus either by insertion of sulfur atoms into P À P bonds or by exocyclic addition to phosphorus atoms. The maximum amount of sulfur per molecule is present in P 4 S 10 . [2] The congruently melting phosphorus sulfides P 4 S 3 , P 4 S 7 , and P 4 S 10 are sy… Show more

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Cited by 20 publications
(9 citation statements)
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“…For K eff = 0 GPa, our simulation in Figure 2b suggests that sulfur in LGPS is the most likely to be oxidized, forming S 0  (P 2 S 7 ) and S 0 (elemental sulfur) above 2.41 V. Note that there are two types of S bonds in polysulfides, the bridging sulfur in PS 0 P with a XPS peak at 163.5 eV and the non‐bridging sulfur in PS at 162.1 eV. [ 25–28 ] XPS peak of bridging S 0  (163.5 eV) or S 0 (163.9 eV) [ 29 ] should show very similar charge state, and obviously higher than S 2− (161.4 eV) [ 29–31 ] in LGPS. Therefore, the large purple peak at 163.4 eV in Figure 2c2 is likely from the oxidized sulfur in S or P 2 S 7 due to the lack of mechanical constriction in the liquid battery cell.…”
Section: Resultsmentioning
confidence: 99%
“…For K eff = 0 GPa, our simulation in Figure 2b suggests that sulfur in LGPS is the most likely to be oxidized, forming S 0  (P 2 S 7 ) and S 0 (elemental sulfur) above 2.41 V. Note that there are two types of S bonds in polysulfides, the bridging sulfur in PS 0 P with a XPS peak at 163.5 eV and the non‐bridging sulfur in PS at 162.1 eV. [ 25–28 ] XPS peak of bridging S 0  (163.5 eV) or S 0 (163.9 eV) [ 29 ] should show very similar charge state, and obviously higher than S 2− (161.4 eV) [ 29–31 ] in LGPS. Therefore, the large purple peak at 163.4 eV in Figure 2c2 is likely from the oxidized sulfur in S or P 2 S 7 due to the lack of mechanical constriction in the liquid battery cell.…”
Section: Resultsmentioning
confidence: 99%
“…They show a ratio of P:S Ͻ 4:10 and are the first well-characterized crystalline polymeric phosphorus polysulfides. [21] Experimental Section P 4 S 3 was prepared by reaction of stoichiometric amounts of the elements, phosphorus (Hoechst, 99.999 %) and sulfur (Chempur, 99.999 %) in an evacuated silica ampoule at 300°C and purified by recrystallization from toluene (Merck, p.A.). Commercial FeCl 3 (Fluka, Ͼ98 %) was purified by sublimation in a stream of chlorine gas at 250°C.…”
Section: Resultsmentioning
confidence: 99%
“…The reaction of P 4 S 3 with sulfur in the presence of a small amount of FeCl 3 yields crystalline a-P 2 S 7 and b-P 2 S 7 . 82 The transesterification of methyl aryl phosphorothioates is catalysed by Cd(II), Mn(II), and Pd(II). 83 Addition of sulfur to a phosphaalkene double bond led to the formation of the 1,2l 3 ,s 3 -thiaphosphirane 16.…”
Section: Group 15/16 Chemistrymentioning
confidence: 99%