Despite substantial evidence of short Au⋅⋅⋅H-X contacts derived from a number of X-ray structures of AuI compounds, the nature of AuI ⋅⋅⋅H bonding in these systems has not been clearly understood. Herein, we present the first spectroscopic evidence for an intramolecular AuI ⋅⋅⋅H+ -N hydrogen bond in a [Cl-Au-L]+ complex, where L is a protonated N-heterocyclic carbene. The complex was isolated in the gas phase and characterized with helium-tagging infrared photodissociation (IRPD) spectra, in which H+ -N-mode-derived bands evidence the intramolecular AuI ⋅⋅⋅H+ -N bond. Quantum chemical calculations reproduce the experimental IRPD spectra and allow to characterize the intramolecular Au⋅⋅⋅H+ -N bonding with a short rAu⋅⋅⋅H distance of 2.17 Å and an interaction energy of approximately -10 kcal mol-1 . Various theoretical descriptors of chemical bonding calculated for the Au⋅⋅⋅H+ -N interaction provide strong evidence for a hydrogen bond of moderate strength.

Centre of Polymer Systems Tomas Bata University in Zlín tř Tomáše Bati 5678 76001 Zlín Czech Republic

Department of General and Inorganic Chemistry Faculty of Chemical Technology University of Pardubice 53210 Pardubice Czech Republic

Department of Organic Chemistry Faculty of Science Charles University Hlavova 2030 8 12843 Prague 2 Czech Republic

Institute for Molecules and Materials Radboud University Heyendaalseweg 135 6525 AJ Nijmegen The Netherlands

Institute of Organic Chemistry and Biochemistry Czech Academy of Sciences Flemingovo náměstí 2 16610 Prague 6 Czech Republic

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Note added in revision: Upon submitting the final version of this manuscript, a paper by M. Rigoulet, S. Massou, E. D. Sosa Carrizo, S. Mallet-Ladeira, A. Amgoune, K. Miqueu, D. Bourissou “Evidence for genuine hydrogen bonding in gold(I) complexes” was published in Proc. Natl. Acad. Sci. USA 2019. , 116, 46–51. The authors report evidence for very similar AuI⋅⋅⋅H+−N hydrogen bonding in cationic gold(I) complexes featuring ditopic phosphine-ammonium (P,NH+) ligands. The presence of Au⋅⋅⋅H−N hydrogen bonding was experimentally delineated by NMR, IR, and XRD and further assessed (and confirmed) computationally. PubMed PMC

1H NMR is not a proof of hydrogen bonds in transition metal complexes