Aurophilic Interactions in [(L)AuCl]···[(L')AuCl] Dimers: Calibration by Experiment and Theory

0489622 - ÚOCHB 2019 RIV US eng J - Journal Article
Andris, E. - Andrikopoulos, Prokopis C. - Schulz, J. - Turek, J. - Růžička, A. - Roithová, J. - Rulíšek, Lubomír
Aurophilic Interactions in [(L)AuCl]···[(L')AuCl] Dimers: Calibration by Experiment and Theory.
Journal of the American Chemical Society. Roč. 140, č. 6 (2018), s. 2316-2325. ISSN 0002-7863. E-ISSN 1520-5126
R&D Projects: GA ČR(CZ) GA17-24155S
Institutional support: RVO:61388963
Keywords : N-heterocyclic carbenes * approximate coulomb potentials * auxiliary basis sets
OECD category: Physical chemistry
Impact factor: 14.695, year: 2018

Attractive metallophilic (aurophilic, argentophilic, cuprophilic, etc.) interactions play an important role in arrangement and stabilization of oligonuclear metal ion complexes. We report a combined experimental and theoretical assessment of aurophilic interactions in closed-shell gold(I) dimers. The experimental binding energies were obtained for charged [(LH)AuCl](+)···[(L')AuCl] dimers (L is either a phosphine or an N-heterocyclic carbene ligand) in the gas phase. These energies served for benchmarking of correlated quantum chemical calculations (CCSD(T)-calibrated SCS-MP2/CBS method) that were then applied to neutral [(L)AuCl]···[(L')AuCl] dimers. The overall attractive interactions between monomeric units are in the order of 100165 kJ mol1 in the charged dimers and of 70-105 kJ mol(-1) in the corresponding neutral dimers. In the neutral dimers, pure aurophilic interactions account for 25-30 kJ mol(-1), the dipoledipole interactions for 30-45 kJ mol(-1), and the L···L' “inter-ligand” dispersion interactions for 5-25 kJ mol(-1). Energy of the aurophilic interactions is thus comparable or even larger than that of strong hydrogen bonds.
Permanent Link: http://hdl.handle.net/11104/0284006