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

Structure and properties of Ge2.5PSx glasses

“…The 31 P spin-lattice relaxation time, T 1 was measured for this sample and found to be 4.3 and 0.8 s for the apical and basal phosphorus, respectively. As a point of comparison, the T 1 values for all other phosphorus sites ranged from 120 to 720 s. The chemical shifts and measured T 1 are identical to values for the plastic phase of P 4 S 3 , which is stable above 41°C [13,14]. In the glass samples, frictional heating due to the high speed of the MAS rotor elevates the sample temperature, so that the P 4 S 3 in the glass undergoes dynamics similar to the plastic phase of pure P 4 S 3 , although in the glasses there is no phase separation.…”

“…As even more sulfur is removed (deficiencies of 20% or greater), however, a new cluster is observed, with signals at 73 and )111 ppm. We assign these signals to the apical and basal phosphorus, respectively, of P 4 S 3 [13,14]. The 31 P spin-lattice relaxation time, T 1 was measured for this sample and found to be 4.3 and 0.8 s for the apical and basal phosphorus, respectively.…”

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.…”

Adduct Compounds (MCl5)2(β-P4Ch4) with M = Nb, Ta and Ch = S, Se

“…Phosphorus and sulfur were heated in 1 : 1 ratio to 330 • C and then rapidly cooled down to ambient temperature to obtain a solidified melt which is a mixture of different phosphorus sulfides [12,13]. …”