- The Kinetics and Mechanism of the Reaction of Tricoordinate Phosphorus Compounds with Diaryl Trisulfides
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Kinetic data and activation parameters are reported for the reaction of a series of tricoordinate phosphorus compounds, , with diaryl trisulfides.The second-order rate coefficients for series of arylphosphines, phosphinites and phosphonites, correlate with the Hammett ? 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.
- Hall, C. Dennis,Tweedy, Bruce R.,Kayhanian, Robert,Lloyd, John R.
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p. 775 - 779
(2007/10/02)
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- Kinetics and mechanism of the reaction of trico-ordinate phosphorus ompounds with octasulphur
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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 Ione-pair orbital on phosphorus and inductive electron donation by the alkyl groups.The rates of reaction of series of arylphosphonites, diarylphosphonites, and triarylphosphones correlate with the Hammett ? constants to give ? values of -3.0, -3.0, and -2.5, respactively, and the results are discussed in terms of the Reactivity-Selectivity Principle and the biphilic mechanism or insertion of trico-ordinate phosphorus into ?-bonds.
- Lloyd, John R.,Lowther, Nicholas,Zsabo, G.,Hall, C. Dennis
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p. 1813 - 1818
(2007/10/02)
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