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

Abstract

The oxidation of phosphorus by sulfur at low temperatures (<100 °C) has been shown to produce complex mixtures that include 12 of the 17 known binary phosphorus sulfides. Two of these 17 sulfides have been observed in these mixtures for the first time. The rate-determining and first step in the reaction appears to be the formation of the S8 diradical. This proposal is supported by the observed rate at which the sulfides are formed and the distribution of the sulfide product stoichiometries. Photoinitiation of this oxidation at 0 °C produces a similar array of sulfides. 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.

Structure and properties of Ge2.5PSx glasses

“…First, a large increase in the amount of network PS 3=2 , at a shift of d iso ¼ 123 ppm [10,11], is observed, which indicates that the nonbridging sulfur in S@PS 3=2 is most easily lost. Furthermore, since PS clusters containing multiple PS 3=2 sites are unstable [12], the cage/cluster signals at 58 ppm and 44 ppm diminish rapidly as well. As even more sulfur is removed (deficiencies of 20% or greater), however, a new cluster is observed, with signals at 73 and )111 ppm.…”

(CuI)3P4S4: Preparation, Structural, and NMR Spectroscopic Characterization of a Copper(I) Halide Adduct with -P4S4

“…Previous attempts to prepare ligand-free a-P 4 S 4 and b-P 4 S 4 from the elements at low temperatures (T < 100 8C) led to a mixture of different phosphorus sulfides, containing the above-mentioned compounds only as minor reaction products. [7] Polycrystalline b-P 4 S 4 has also been obtained by the reaction of P 4 S 5 and P(C 6 H 5 ) 3 in cold CS 2 , [8] and its molecular structure has been derived from 31 P NMR spectroscopic data only. [9] Herein we report the preparation and structural characterization of (CuI) 3 P 4 S 4 .…”

The Crystal and Molecular Structure of γ‐P4S6

“…The compound crys- [6, [13][14][15] tallizes as a pseudomerohedral twin in the monoclinic space group P2 1 /m (No. 11) with a = 6.627(3) Å, b = 10.504(7) Å, c = 6.878(3) Å and β = 90.18(4)°.…”

“…Among these, only the crystal structure of β-P 4 S 6 was determined by X-ray diffraction analysis. [6] On the contrary the structures of α-P 4 S 6 , [13] γ-P 4 S 6 , [14] δ-P 4 S 6 , and ε-P 4 S 6 [15] have been characterized only spectroscopically. γ-P 4 S 6 has first been observed by Jason as a product in the oxidation of phosphorus by sulfur at low temperatures (Ͻ 100°C) and in the sulfurization of α-P 4 S 5 by triphenylarsenic sulfide.…”

“…γ-P 4 S 6 has first been observed by Jason as a product in the oxidation of phosphorus by sulfur at low temperatures (Ͻ 100°C) and in the sulfurization of α-P 4 S 5 by triphenylarsenic sulfide. [14] Based on the signals in the corresponding solution 31 P NMR spectra he was able to assign a molecular structure. Herein, we confirm the molecular structure assigned by Jason, and in addition, present the crystal structure of γ-P 4 S 6 .…”