Phosphorus oxide sulfides

Two general routes for the preparation of phosphorus oxide sulfides are reported in the literature  

The preparative challenge in both cases is the exact adjustment of the experimental parameters in order to obtain the desired species as the major product. 

Crystal and Molecular Structures 1. Crystal and Molecular Structure of P4OeS4 

The molecular structure of P406S4 in the gaseous state was determined in 1939 by means of electron diffraction (176). Its crystal structure was determined by X-ray diffraction (177) and refined on the basis of diffractometer data in order to obtain state-of-the-art structural parameters (80). The bond lengths and angles obtained in these three investigations are listed in Table XXL 

The structures of pure P406S, P406S2, and P406S3 in the solid state were determined (166,175). The structural data obtained are listed in Tables XXII and XXIII. The P406 cage is made to contract by successive addition of sulfur atoms, as can be seen in Table XXIV, in which the 

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Phosphorus oxides, sulfides, selenides and related compounds... 

Molecular Packings of the Phosphorus Oxide Sulfides P4OeSn (n = 0—4) in the Solid State... 

The phosphorus oxide sulfide P403S6 has been described by G. U. Wolf and M. Meisel (178) shows an A3X-type 31P NMR spectrum with signals at +46.0 ppm [P(III)] and + 55.7 ppm [P(V)], the coupling constant being 108 Hz. This corresponds to the molecular structure described in Section III.B. 

Comparison of the Observed and Calculated 31P NMR Data of Phosphorus Oxide Sulfides P406S (n = 0-4) (162)... 

Fig. 22. Schematic representation of the 31P shielding tensors of phosphorus oxide sulfides (162).

Fig. 2. Structures of phosphorus oxides, sulfides, and oxysulfldes [from King (S)].

D. Theoretical Studies Molecular Phosphorus Oxide Sulfides... 

The P NMR spectra of the remaining phosphorus oxide sulfides were recorded using solutions that in most cases contained mixtures of these compounds (77). The chemical shifts and coupling constants... 

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