Reactions of phosphorus trifluoride with anionic nucleophiles in the gas phase

Abstract

The kinetics and products of a range of reactions between 14 different anions and phosphorus trifluoride were studied in a flowing afterglow 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, phosp..