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Preparing Gold(I) for Interactions with Proton Donors: The Elusive [Au]⋅⋅⋅HO Hydrogen Bond
Author(s) -
Groenewald Ferdinand,
Dillen Jan,
Raubenheimer Helgard G.,
Esterhuysen Catharine
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201508358
Subject(s) - carbene , steric effects , hydrogen bond , chemistry , molecule , stereochemistry , crystallography , medicinal chemistry , computational chemistry , catalysis , organic chemistry
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 H 2 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.