Synthesis and characterisation of trimethylsilyl phosphorohalidates: Me3SiOP(O)FX (X = Cl, Br) and (Me3SiO)(2)P2O3F2

Trimethylsilyl phosphorochloridofluoridate, Me3SiOP(O)FCl, has been prepared by reaction of POFCl2 with hexamethyldisiloxane or by treatment of bis(trimethylsilyl) phosphorofluoridate with phosphorus pentachloride. The compound could be purified by vacuum distillation and has been isolated in 55% yi...

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Bibliographic Details
Published inJournal of fluorine chemistry Vol. 125; no. 1; pp. 83 - 90
Main Authors Rovnanik, P, Cernik, M
Format Journal Article
LanguageEnglish
Published LAUSANNE Elsevier 01.01.2004
Subjects
Chemistry
Chemistry, Inorganic & Nuclear
Chemistry, Organic
Physical Sciences
Science & Technology
HALIDES
phosphorobromidofluoridate
thermal decomposition
FLUORPHOSPHORVERBINDUNGEN
ACIDS
DIFLUOROPHOSPHATE
condensation reactions
VIBRATIONAL-SPECTRA
SBCL5
phosphorochloridofluoridate
trimethylsilyl esters
ESTERS
TICL4
diphosphorodifluoridate
ORGANOPHOSPHORUS COMPOUNDS
ASSIGNMENTS
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Summary:Trimethylsilyl phosphorochloridofluoridate, Me3SiOP(O)FCl, has been prepared by reaction of POFCl2 with hexamethyldisiloxane or by treatment of bis(trimethylsilyl) phosphorofluoridate with phosphorus pentachloride. The compound could be purified by vacuum distillation and has been isolated in 55% yield. The ester Me3SiOP(O)FBr is formed in an analogous reaction of POFBr2 with (Me3Si)(2)O, however its susceptibility to spontaneous decomposition makes its isolation unfeasible. Condensation of Me3SiOP(O)FCl with (Me3SiO)(2)P(O)F or heating of POFBr2 with excess hexamethyldisiloxane gave bis(trimethylsilyl) diphosphorodifluoridate, (Me3SiO)(2)P2O3F2, in 45-53% yield. The existence of both expected diastereoisomers was revealed by F-19 and P-31 NMR spectroscopy. (C) 2003 Elsevier B.V. All rights reserved.
ISSN:0022-1139
1873-3328
DOI:10.1016/j.jfluchem.2003.10.006