The kinetics and mechanism of the reaction of tricoordinate phosphorus compounds with diaryl trisulfides

Abstract

Kinetic data and activation parameters are reported for the reaction of a series of tricoordinate phosphorus compounds, [Ar_nP(OR)_3–n], with diaryl trisulfides. The second-order rate coefficients for series of arylphosphines, phosphinites and phosphonites, correlate with the Hammett σ constants of the aryl substituents with ρ values of –1.1, –1.1 and –1.1 respectively and these results are discussed in terms of a biphilic mechanism analogous to that proposed for the reaction of tricoordinate phosphorus with S₈.