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

Journal Article · Wed Jan 02 00:00:00 EST 1991 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00001a005· OSTI ID:5289839

Bjorholm, T ^[1]; Jakobsen, H J ^[2]

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1. Cheminova A/S, Lemvig (Denmark)
2. Univ. of Aarhus (Denmark)

High-temperature 1D and 2D exchange {sup 31}P-NMR spectra of melts of pure and well-defined phosphorus sulfides shown that, e.g., {beta}-P{sub 4}S{sub 5} or mixtures of P{sub 4}S{sub 3} and sulfur transform into mixtures of at least eight different P{sub 4}S{sub n} (n = 3-7) species which are identified and quantified. Transformations and exchange pathways between the different P{sub 4}S{sub n} species in the melts are revealed by the 2D exchange {sup 31}P-NMR spectra at 225-250 C. Furthermore, the exchange correlations observed from these spectra yield unambiguous assignments of the unknown or earlier incorrectly assigned {sup 31}P chemical shifts for {beta}-P{sub 4}S{sub 6}, {beta}-P{sub 4}S{sub 5}, {alpha}-P{sub 4}S{sub 5}, and a new P{sub 4}S{sub 6} isomer ({alpha}-P{sub 4}S{sub 6}). 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 {beta}-P{sub 4}S{sub 5} and {beta}-P{sub 4}S{sub 6} (the predominant species in the {beta}-P{sub 4}S{sub 5} melt and isolated here for the first time) have been isolated and characterized by high-speed {sup 31}P MAS-NMR spectroscopy.

• OSTI ID: 5289839
• Journal Information: Journal of the American Chemical Society; (United States), Vol. 113:1; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
PHOSPHORUS SULFIDES
NUCLEAR MAGNETIC RESONANCE
CHEMICAL SHIFT
EXPERIMENTAL DATA
HIGH TEMPERATURE
MEASURING METHODS
CHALCOGENIDES
DATA
INFORMATION
MAGNETIC RESONANCE
NUMERICAL DATA
PHOSPHORUS COMPOUNDS
RESONANCE
SULFIDES
SULFUR COMPOUNDS
400201* - Chemical & Physicochemical Properties