Reactions of phosphorus trifluoride with anionic nucleophiles in the gas phase

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Eur. J. Mass Spectrom. 2, 225 - 231 (1996)

Reactions of phosphorus trifluoride with anionic nucleophiles in the gas phase

Jacob D. Smith and Richard A.J. O'Hair
Department of Chemistry, Kansas State University, Manhattan, KS 66, USA.

ABSTRACT:

The kinetics and products of a range of reactions between 14 different anions and phosphorus trifluoride were studied in a flowing after glow apparatus.These reactions are best rationalized as proceeding via a mechanism involving initial attack by the anion (Nu) at phosphorus to form an energized tetracoordinate anion intermediate [NuPF₃], which either undergoes collisional stabilization with helium or undergoes fragmentation via loss of HF if the original anion contains an acidic proton(s). This study suggests that PF₃ is a general and useful reagent for the gas-phase synthesis of a range of phosphorus containing anions with phosphoruscarbon, phosphorusnitrogen, phosphorusoxygen, phosphorussilicon and phosphorussulfur bonds.

Keywords:

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