150034-67-6Relevant academic research and scientific papers
THE KINETICS AND MECHANISM OF THE REACTION OF TRICO-ORDINATE PHOSPHORUS COMPOUNDS WITH TETRACYANOQUINODIMETHANE AND TETRACYANOETHYLENE
Hall, C. D.,Beer, P. D.,Powell, R. L.,Naan, M. P.
, p. 145 - 156 (2007/10/02)
Trico-ordinate phosphorus compounds, ArnP(OPri)3-n where n = 0-3, react with tetracyanoquinodimethane (TCNQ) in acetonitrile in the presence of water to give the corresponding phosphoryl compounds, ArnP(O)(OPri)3-n and 1,4-bis-dicyanomethylbenzene (TCNQH2) in quantitative yield.The kinetics of these reactions are reported together with the Hammett ρ-parameters from variation of substituents in the aryl group for n = 1,2 and 3.On the basis of the available evidence, a mechanism is proposed involving one electron transfer from phosphorus (the donor) to TCNQ.A kinetic study of the reaction of triarylphosphines with TCNE in aqueous acetonitrile, however, suggests rate-limiting nucleophilic attack on nitrogen rather than the radical cation mechanism.Key words: Tricoordinate phosphorus, tetracyanoquinodimethane, tetracyanoethylene, kinetics, mechanism.
The Kinetics and Mechanism of the Reaction of Tricoordinate Phosphorus Compounds with Diaryl Trisulfides
Hall, C. Dennis,Tweedy, Bruce R.,Kayhanian, Robert,Lloyd, John R.
, p. 775 - 779 (2007/10/02)
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.
