REACTION-MECHANISMS OF PHOSPHORUS FLUORIDES - AN AB-INITIO STUDY

Reaction mechanisms of phosphorus fluorides may be analyzed on the bas is of the coordination model of reaction mechanisms. Some of the inter mediates and mechanistic details arising out of such an analysis have been investigated by ab initio molecular orbital calculations. The rap id equilibrium between five- and six-coordinate phosphorus fluorides, and exchange of axial and equatorial fluorines in PF5, is investigated by calculating the structures of adducts of phosphorus pentafluoride, i.e. D-PF5 where D=NH3, H2O, CH3F, HF, PF5 and PF6-. Bond cleavage in phosphorus fluorides is investigated by calculating the structure of a fluorine-bridged anion P2F11-. A reaction pathway is proposed for th e fluoride-catalyzed oxidation of phosphorus(III) to phosphorus(V) flu orides which involves the known species PF3, PF4-, PF4. and PF5. (C) E lsevier Science S.A.