Van der Waals Complexes of Cu, Ag, and Au with Hydrogen Sulfide. The Bonding Character

Abstract

The electronic and structural features of the Cu···SH₂, Ag···SH₂, and Au···SH₂ complexes are investigated by using the spin-adapted restricted open-shell HF coupled cluster CCSD(T) method combined with the second-order spin-free Douglas−Kroll−Hess (DKH) relativistic approach. M···SH₂ complexes are nonplanar with bonding energies −5.99, −1.99, and −9.08 mHartree, respectively. Comparison with analogous M···OH₂ and M···NH₃ complexes allows us to establish general features of the bonding between coinage metal atoms and ligand molecules with the participation of their lone electron pairs. Consistent interpretation of the interaction effects can be obtained by using the molecular orbital picture of the M···L region. The bonding character is explained by stressing the importance of the charge transfer from the lone pair of the ligand to the metal atom. Relativistic changes of the metal element electron affinity and polarizability facilitate the understanding of major trends in the pattern of interactions between the coinage metal atoms and different lone pair donating ligands.