Halides thiophosphoryl

Table 12.4 Some phosphoryl and thiophosphoryl halides and pseudohalides...

In addition to the monophosphorus phosphoryl and thiophosphoryl compounds discussed above, several poly-phosphoryl and -thiophosphoryl halides have been characterized. Pyrophos-phoryl fluoride, 0=PP2—O—P(=0)p2 (mp —0.1°, bp 72° extrap) and the white crystalline cyclic tetramer [0=P(F)—0)4 were... 

Grignard reactions have been used in the preparation of l-(dialkyl-phosphinyl)- ,3-dienes, e.g. (11), which are intermediates in the synthesis of antiflame polymers. Double-resonance n.m.r. techniques have been applied to the study of the reactions between thiophosphoryl halides and Grignard reagents. For example, the reaction between methylmag-nesium iodide and t-butyldibromophosphine sulphide gave the mixed... 

The reactions between 3-trifluorophenylhydrazine and various halides of both tetracoordinate phosphorus (including thiophosphoryl halides, and MeP(S)Cl2) and acyclic and cyclic chlorides of... 

The oxysulphide P4O6S4, formed by heating P4O6 with sulphur, forms a tetrahedral molecule similar to that of P4O10. The P—S bond length (1-85 A) is similar to that in the thiophosphoryl halides. 

Primary phosphorothiosulphenamides may be acylated, and with sodium ethoxide they are converted into trialkyl phosphorothionates. Other reactions of phosphorothiosulphenamides include the loss of sulphur upon treatment with sodium, and translocation of the amino-function when treated with thiophosphoryl halides. Treatment of the acyl chloride (71) with ethyleneimine gives an amide which undergoes ready conversion into the isocyanate (72). ... 

Thiophosphoryl halides, XjP S (X = Cl, Br), are weaker donors than Cl3P=0 and Ph3P=S. Only a few complexes are known [C13PS-AICI3], [Br3RS-AlBrj], [CljPS-SbCls] and [BrjPS-SbCIs]. The ligands are S-bonded, as v(P=S) decreases from 748 to ca. 650 cm and v(P-X) increases with adduct formation." ... 

Vibrational data for the mked phosphoryl and thiophosphoryl halides have been analysed to give force constants and thermodynamic data. Electron-diffraction data show that the most probable conformation for trimethylene chlorophosphite (52) is a chair with the chlorine atom in an... 

Reaction of thiophosphoryl halides with Ag foil at 1100% K leads to the formation of X-P= S molecules (X = F,Cl,Br) which can be characterised by matrix isolation. Ozone oxidation leads to planar thioxophosphoranes [8 ](9.633, cf. Chapter 4.6). 

Selenophosphoryl halides, PSeX3, are more difficult to obtain than thiophosphoryl halides. Direct addition of Se and PF3 occurs at 300°C and 4000 atm but the product is light-sensitive and readily dissociates at normal temperatures and pressures. 

A.F. Childs, The thiophosphoryl halides, in Mellor s Comprehensive Treatise on Inorganic and Theoretical Chemistry, Vol. 8, Suppl 3, Longmans, London, 1971. 

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