76943-18-5Relevant academic research and scientific papers
The kinetics and mechanism of the reaction of tricoordinate phosphorus compounds with sulfenate esters
Hall, C. Dennis,Tweedy, Bruce R.,Lowther, Nicholas
, p. 341 - 358 (2007/10/03)
The kinetics and mechanism of the reaction of tricoordinate phosphorus compounds, ArnP(OCH2CF3)3-n with arylsulfenate esters, ArSOCH2CF3, are reported. Product analysis, kinetic order, activation parameters, Hammett data and solvent effects are the criteria used to elucidate the two step mechanism involving arylthiophosphoranes as intermediates.
THE THERMOLYTIC DECOMPOSITION OF ACYCLIC PHOSPHORANES
Lowther, Nicholas,Crook, Polly,Hall, C. Dennis
, p. 195 - 204 (2007/10/02)
The thermolytic decomposition of acyclic phosphoranes, ArnP(OCH2CF3)5-n in aprotic media has been shown by kinetic studies to proceed via rate-limiting ionization of the phosphoranes.Activation parameters, deuterium isotope effects, solvent effects and ρ-values (for n = 3 and n = 1) support this concept which is consistent with the observed rate-sequence of n = 3> n = 2 > n = 1 > n = 0.Key words: Phosphoranes, thermolysis, kinetics, mechanism.
INHIBITION OF PSEUDOROTATION IN SOME MONOCYCLIC PENTAOXYPHOSPHORANES
Abdou, Wafau M.,Denney, Donald B.,Denney, Dorothy Z.,Pastor, Stephen D.
, p. 99 - 108 (2007/10/02)
Phosphoranes were prepared by allowing 2,4,8,10-tetra-tert-butyl-6-(2,2,2-trifluoroethoxy)-12H-dibenzodioxaphosphocin, the analogous ethoxy compound, 2,4,8,10-tetra-tert-butyl-6-(2,2,2-trifluoroethoxy)-dibenzodioxaphosphepin and the analogous compound without tert-butyl groups to react with trifluoroethyl benzenesulfonate.The first three phosphoranes showed significant barriers to intramolecular ligand reorganization, 14-16 kcal/mole.The phosphorane without the tert-butyl groups had a barrier too low to measure.These observations are discussed in terms of steric inhibition of pseudorotation.
