Configurational stability of chlorophosphines.
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-1). Further calculations and experiments on the halogen exchange with HBr corroborate this mechanism, with bromophosphines being formed instantaneously. Finally, to avoid the racemization, the borane is found to be a very promising protecting group for the configurational stability of the P-chirogenic chlorophosphines.
Humbel
Stéphane
S
Groupe Modélisation & Réactivité Chimique, UMR 6519, CNRS et Université de Reims, Moulin de la Housse, BP 1039, 51687 Reims, France. stephane.humbel@univ.u-3mrs.fr
Bertrand
Cyrille
C
Darcel
Christophe
C
Bauduin
Christophe
C
Jugé
Sylvain
S