Theoretical study of the interaction d10-s2 between Pt(0) and metals on the [Pt(PH3)3M] complexes (M = Hg(0), Au(-I))

We studied the attraction between [Pt(PH3)(3)] and the metals (Hg(0) and Au(-I)) in the hypothetical [Pt(PH3)(3)M] isoelectronic complexes using ab initio methodology. We found that the changes around the equilibrium distance Pt-M and in the interaction energies are sensitive to the electron correlation potential. This effect was evaluated using several levels of theory, including HF, MPn (n=2-4), CCSD and CCSD(T). In the [Pt(PH3)(3)Hg] complex, at the different methodology levels are obtained interaction energies at the equilibrium distance R-e (Pt-Hg) range from 10 to 42 kJ/mol. Such magnitude are in the order of a metallophilic interaction. On the other hand, in the [Pt(PH3)(3)Au](-) complex, the interaction energies An Pt are range from 35 to 129 kJ/mol, beyond the metallophilic interaction. At long-distances, the behaviour of the [Pt(PH3)(3)-M] interaction may be related mainly to electrostatic, charge-induced dipole and dispersion terms, involving the individual properties of [Pt(PH3)(3)] and the individual metals. The dispersion term (R-6) is found as the principal contribution in the stability at the long and short distances in the [Pt(PH3)(3)Hg] complex. While in [Pt(PH3)(3)Au](-) complex, the electrostatic and charge-induced dipole terms are found as the principal contributions in the stability at the long distances. (c) 2006 Elsevier B.V. All rights reserved.