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Kinetics and mechanism of the reaction of trico-ordinate phosphorus compounds with octasulphur

1985; Royal Society of Chemistry; Issue: 11 Linguagem: Inglês

10.1039/p29850001813

2050-8239

John R. Lloyd, Nicholas Lowther, G. Zsabo, C. Dennis Hall,

Chemical Reaction Mechanisms

Kinetic data and activation Parameters are reported for the reactions of a series of phosphites, arylphosphonites, diarylphosphinites, and triarylphosphines with octasulphur (S8) in toluene as solvent. For the Phosphites the data are explained in terms of changes in p-character of the lone-pair orbital on Phosphorus and inductive electron donation by the alkyl groups. The rates of reaction of series of arylphosphonites, diarylphosphinites, and triarylphosphines correlate with the Hammett σ constants to give ρ values of –3.0, –3.0, and –2.5, respectively, and the results are discussed in terms of the Reactivity–Selectivity Principle and the biphilic mechanism for insertion of trico-ordinate phosphorus Into σ-bonds.