Non-Covalent Interactions of the Lewis Acids Cu–X, Ag–X, and Au–X (X = F and Cl) with Nine Simple Lewis Bases B: A Systematic Investigation of Coinage–Metal Bonds by Ab Initio Calculations

Abstract

The equilibrium geometry and two measures (the equilibrium dissociation energy in the complete basis set limit, De(CBS) and the intermolecular stretching force constant kσ) of the strength of the non-covalent interaction of each of six Lewis acids M–X (M = Cu, Ag, Au) with each of nine simple Lewis bases B (B = N2, CO, HCCH, CH2CH2, H2S, PH3, HCN, H2O, and NH3) have been calculated at the CCSD(T)/aug-cc-pVTZ level of theory in a systematic investigation of the coinage–metal bond. Unlike the corresponding series of hydrogen-bonded B⋯HX and halogen-bonded B⋯XY complexes (and other series involving non-covalent interactions), De is not directly proportional to kσ. Nevertheless, as for the other series, it has been possible to express De in terms of the equation De = cNB.EMX, where NB and EMX are the nucleophilicities of the Lewis bases B and the electrophilicities of the Lewis acids M–X, respectively. The order of the EMX is determined to be EAuF > EAuCl > ECuF > ECuCl > EAgF ≈ EAgCl. A reduced electrophilicity defined as (EMX/σmax) is introduced, where σmax is the maximum positive value of the molecular electrostatic surface potential on the 0.001 e/bohr3 iso-surface. This quantity is, in good approximation, independent of whether F or Cl is attached to M.