Reactions of phosphorus trifluoride with anionic nucleophiles in the gas phase

Eur. J. Mass Spectrom. 2, 225–231 (1996)
DOI: 10.1255/ejms.56

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 66506-3701, 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 phosphorus–carbon, phosphorus–nitrogen, phosphorus–oxygen, phosphorus–silicon and phosphorus–sulfur bonds.

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