ChemPhysChem 20, 1572–1580 (2019)

DOI: 10.1002/cphc.201900354

Understanding Regium Bonds and their Competition with Hydrogen Bonds in Au2:HX Complexes

A theoretical study of the regium and hydrogen bonds (RB and HB, respectively) in Au2:HX complexes has been carried out by means of CCSD(T) calculations. The theoretical study shows as overall outcome that in all cases the complexes exhibiting RB are more stable that those with HB. The binding energies for RB complexes range between −24 and −180 kJ ⋅ mol−1, whereas those of the HB complexes are between −6 and −19 kJ ⋅ mol−1. DFT‐SAPT also indicated that HB complexes are governed by electrostatics, but RB complexes present larger contribution of the induction term to the total attractive forces. 197Au chemical shifts have been calculated using the relativistic ZORA Hamiltonian.