Intramolecular C–N bond activation by a geometrically constrained PIII-centre

Abstract

In this work the first examples of C–N bond activation by insertion into a geometrically constrained P^III-centre are shown. The mechanisms of these activation processes leading to new P^V species were studied both experimentally and computationally. Interestingly, in the case of insertion of the P^III-centre into an N–C(O)H bond, an unstable phosphoranyl-formaldehyde intermediate is probably formed, which undergoes decarbonylation in the presence of a catalytic amount of HCl producing a hydrophosphorane.