Configurational Stability of Chlorophosphines
Résumé
The configurational stability of chlorophosphines is investigated. Several mechanisms involving chlorophosphine monomer, dimers and adducts with HCl are evaluated by Density Functional Theory calculations. The presence of HCl in the medium is found to catalyze the P-center chiral inversion at room temperature. The reaction involves a two-step mechanism with low transition states (10 kcal.mol-1) and a stabilized achiral intermediate (-2.6 kcal.mol-2-1). Further calculations and experiments on the halogen exchange with HBr corroborate this mechanism, with bromophosphines being formed instantaneously.
Domaines
Chimie théorique et/ou physique
Origine : Fichiers produits par l'(les) auteur(s)