X. Lopez et al., CHARACTERIZATION OF (P(-MOLECULE CLUSTERS OF FIRST-ROW HYDRIDES()L(X))L(Y) ION), Journal of the American Chemical Society, 118(11), 1996, pp. 2718-2725
Ab initio calculations of phosphorus ionic clusters of the type PL(+).
L, PL(2)(+). L, PL(3)(+), and PL(4)(+), with L = NH3, OH2, and FH, in
both triplet and singlet states have been carried out, in order to de
termine their geometries and binding energies. The nature of the bindi
ng has also been extensively studied by means of both the topological
analysis of the total electron charge density and the natural bond orb
ital analysis. When the ligand is bound as a second ligation shell thr
ough a formal hydrogen bond, significant cooperative effects between t
he two ligand shells have been detected. Substantial covalency is foun
d for these hydrogen bonds, along with the weakening of the hydride bo
nd with the inner ligand and the reinforcing of the bond between the i
nner ligand and the phosphorus. These processes are greatly favored fo
r the singlet state of the phosphorus, and for the case of ammonia and
water ligands, conversion reactions leading to PXH(n-1). XH(n+1)(+) c
omplexes are observed. It has been found that the maximum number of li
gands bound to (P-3P+ is two, whereas that maximum is ligand dependent
in the case of (D-1P+, with two for NH3, three for OH2, and four for
FH. We have also observed that soft ligands present a sharp decrease i
n successive binding energies to phosphorus, whereas hard ligands show
smoother variations. Finally, for most cases, the addition of the new
ligand as a second ligation shell is favored with respect to the dire
ct addition to the phosphorus, since cooperative effects make more eff
icient the donation of electronic charge to the phosphorus ion.