Inorganic chemistry of fluorocarbenes. 1. Reactions of tetrafluoroethylidene with fluorine-containing phosphines

Article abstract of DOI:10.1021/ic50161a045

The interactions of tetrafluoroethylidene with three fluorine-containing phosphines have been investigated. The source of the carbene is the pyrolytic decomposition of C₂F₅SiF₃ at 200°C. The reaction of CF₃CF with PF₃ generates CF₂=CFPF₄ and PF₅; reaction with (CF₃)₃P leads to (CF₃)₂PCF(CF₃)₂; and reaction with (CF₃)₂PCF(CF₃)₂ produces the fluorocarbon (CF₃)₂CFCF(CF₃)₂. The possibility that the vinylphosphorane product of the PF₃ reaction results from fluorine-transfer rearrangement of C₂F₅PF₂ as an intermediate product was discredited by a demonstration that C₂F₅PF₂ is thermally stable under the reaction conditions. Other mechanistic pathways are discussed.