Intramolecular C-N bond activation by a geometrically constrained P III -centre.

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.