Spectroscopic and Computational Evidence of Intramolecular AuI⋅⋅⋅H+−N Hydrogen Bonding

The ties that bind: Spectroscopic evidence of a rare example of a Au⋅⋅⋅H⁺−N hydrogen bond is reported. Computational investigations confirm the nature of the hydrogen bond to gold(I).

Abstract

Despite substantial evidence of short Au⋅⋅⋅H−X contacts derived from a number of X‐ray structures of Au^I compounds, the nature of Au^I⋅⋅⋅H bonding in these systems has not been clearly understood. Herein, we present the first spectroscopic evidence for an intramolecular Au^I⋅⋅⋅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 Au^I⋅⋅⋅H⁺−N bond. Quantum chemical calculations reproduce the experimental IRPD spectra and allow to characterize the intramolecular Au⋅⋅⋅H⁺−N bonding with a short r _Au⋅⋅⋅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.

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