Ab initio localized orbital calculations of the bonding in phosphines and phosphine complexes
Abstract
Localized orbital calculations of the bonding in the phosphines PH3, PMe3, PF3 and PCl3 and the phosphine complexes PH3O, PF3O, PMe3O, PCl3O, PH3BH3, PF3BH3 and PF3S are described using the unitary transform of Boys. A description of the bonding in terms of lone pairs and bond pairs is obtained and the nature of d orbital participation in these molecules is shown. In the phosphines (PX3), 3d functions participate only in the P—X bond orbitals, whilst in the oxides the three equivalent P—O bonding orbitals involve the phosphorus 3d functions. The boranes have a single P—B bond involving the valence p orbitals of the two atoms.