Hm. Senn et al., Phosphane lone-pair energies as a measure of ligand donor strengths and relation to activation energies, J MOL ST-TH, 506, 2000, pp. 233-242
Using density-functional theory as implemented in the projector-augmented w
ave method, we have calculated structures, energy levels, structures of the
protonated forms, and proton affinities of the phosphanes PH3, PF3, P(CF3)
(3), PMe3, P(NMe2)(3), P(C6H5)(3), P(p-C6H4OMe)(3), and P(P-C6H4NMe2)(3) Th
e donor strengths of the phosphanes are discussed in terms of lone-pair ene
rgies and proton affinities. The influence of the donor ability of the phos
phane ligands on the protonolytic cleavage of the metal-carbon bond in [NiC
l(CH2CH2NH3)(PR3)(2)](+) complexes has been studied. A linear relationship
between the lone-pair energies of the phosphanes and the activation barrier
has been established. (C) 2000 Elsevier Science B.V. All rights reserved.