Preparing Gold(I) for Interactions with Proton Donors: The Elusive [Au]⋅⋅⋅HO Hydrogen Bond

Ferdinand Groenewald; Jan Dillen; Helgard G Raubenheimer; Catharine Esterhuysen

doi:10.1002/anie.201508358

Preparing Gold(I) for Interactions with Proton Donors: The Elusive [Au]⋅⋅⋅HO Hydrogen Bond

Angew Chem Int Ed Engl. 2016 Jan 26;55(5):1694-8. doi: 10.1002/anie.201508358. Epub 2015 Dec 22.

Authors

Ferdinand Groenewald¹, Jan Dillen¹, Helgard G Raubenheimer¹, Catharine Esterhuysen²

Affiliations

¹ Department of Chemistry and Polymer Science, University of Stellenbosch, Private Bag X1, Matieland, 7602, South Africa.
² Department of Chemistry and Polymer Science, University of Stellenbosch, Private Bag X1, Matieland, 7602, South Africa. ce@sun.ac.za.

PMID: 26695099
DOI: 10.1002/anie.201508358

Abstract

MP2 and DFT calculations with correlation consistent basis sets indicate that isolated linear anionic dialkylgold(I) complexes form moderately strong (ca. 10 kcal mol(-1) ) Au⋅⋅⋅H hydrogen bonds with single H2 O molecules as donors in the absence of sterically demanding substituents. Relativistic effects are critically important in the attraction. Such bonds are significantly weaker in neutral, strong σ-donor N-heterocyclic carbene (NHC) complexes (ca. 5 kcal mol(-1) ). The overall association (>11 kcal mol(-1) ), however, is strengthened by co-operative, synergistic classical hydrogen bonding when the NHC ligands bear NH units. Further manipulation of the interaction by ligands positioned trans to the carbene, is possible.

Keywords: ab initio calculations; dihydrogen bonds; gold; hydrogen bonds.

Publication types

Research Support, Non-U.S. Gov't