title: Preparing Gold(I) for Interactions with Proton Donors: The Elusive [Au]⋅⋅⋅HO Hydrogen Bond.
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.
authors.affiliation: Department of Chemistry and Polymer Science, University of Stellenbosch, Private Bag X1, Matieland, 7602, South Africa.
authors.forename: Ferdinand
authors.initials: F
authors.lastname: Groenewald
authors.affiliation: Department of Chemistry and Polymer Science, University of Stellenbosch, Private Bag X1, Matieland, 7602, South Africa.
authors.forename: Jan
authors.initials: J
authors.lastname: Dillen
authors.affiliation: Department of Chemistry and Polymer Science, University of Stellenbosch, Private Bag X1, Matieland, 7602, South Africa.
authors.forename: Helgard G
authors.initials: HG
authors.lastname: Raubenheimer
authors.affiliation: Department of Chemistry and Polymer Science, University of Stellenbosch, Private Bag X1, Matieland, 7602, South Africa. ce@sun.ac.za.
authors.forename: Catharine
authors.initials: C
authors.lastname: Esterhuysen
keywords: ab initio calculations; dihydrogen bonds; gold; hydrogen bonds