Phosphinidene generation from phosphorus heterocycles and cages - A theoretical study

The dissociation properties of several phosphorus heterocycles and cages (complexes of phosphinidenes with P-donor ligands) were investigated using DFT methods. Good correlations have been found between the dissociation energies of the complexes with P and N ligands. The comparison with N-donor complexes revealed that the stability of complexes with pyrido-annelation(s) is very similar. The trends in dissociation energies for the benzannelated complexes are identical; however, the complexes with P ligands are much more stable than those with N ligands. The major reason for the different behavior is the pyramidality of the bridgehead P/N atoms in these complexes.