A comparison of metallophilic attraction in (X–M–PH3)2 (M = Cu, Ag, Au; X = H, Cl)

Abstract

Energy partitioning schemes have been used to investigate the metallophilic attraction between gold, silver and copper atoms in model dimers of H–M–PH₃ and Cl–M–PH₃ type. Attraction between the monomers is found to be largest for M = Au, but the reduction from Au to Ag (Cu) is not more than 10–20% (25–35%). Equilibrium M–M distances, r_e(M–M), decrease by 0.2–0.3 Å from Au to Cu, and by 0.1–0.2 Å from Cl to H. An analysis of the intermolecular interaction energy shows that at r_e(M–M) dispersive and non-dispersive components are about equally important for all systems considered. However, the contribution due to metal nd–nd interaction falls drastically from 43% (35%) for Au, over 30% (27%) for Ag, to 18% (13%) for Cu in the H (Cl) compounds.