Phosphoryl and thiophosphoryl halides

POCI3 and certain other molecules mentioned below react with some tetra- and penta-halides to form molecules in which an octahedral group around the metal atom has been completed by one or two 0 atoms of POCI3 (or other) molecules. 

Molecular structures (a) SbCls.POCla, (b) SnCU. 2 POCI3, (c) (TiCU. POCl3)2 

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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... 

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... 

The simple alkyl and aryl-thio phosphorus derivatives, (RS)gP, (RS)aPO and (RS)gPS, can readily be prepared from phosphorus trichloride (or phosphorus pentachloride), phosphoryl chloride or thiophosphoryl chloride, and the corresponding lead thiolate Partially substituted compounds, such as ClxP(SCFa)3 j, are sometimes formed . Substituted derivatives R2P(SRi) and RP(SR )2 can be prepared from the corresponding halide and lead thiolate - " . Various mixed fluorophosphoranes, such as MePF2(SEt)2, can be prepared from MePF4 and ethanethiol or its sodium salt . 

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