Mechanism and kinetics of the reaction of F with trivalent phosphorus iodide using electron spin resonance detection

Abstract

The reaction of iodobistrifluoromethylphosphine, P(CF 3) 2I, with atomic fluorine was studied by fast-flow ESR methods. The initial stage of the reaction is the abstraction of I by F, to form IF with a bimolecular rate constant of (1.0 ± 0.3) × 10 14 cm 3 mol −1 s −1 at 297 K. In the presence of excess F, stepwise addition to the phosphorous occurs. In the presence of excess P(CF 3) 2I, the reaction P(CF 3) 2 + IF → P (CF 3) 2F + I appears to take place. This reaction rate is slow relative to P(CF 3) 2 + F → P(CF 3) 2F.