Gold(III)-Substituted Carbenes
The Au(III)-substituted diazo compounds (N^C^C)AuC(N<sub>2</sub>)R (R = Dmp = 2,6-dimesitylphenyl and SiMe<sub>3</sub>) <b>1</b> and <b>6</b> were synthesized by reacting the (N^C^C)AuCl precursor with the corresponding lithiated diazo compounds. Dinitrogen extrusion was then promoted by UV-vis irradiation. The (N^C^C)Au-C-Dmp carbene <b>3</b> undergoes intramolecular C-H insertion followed by β-H elimination, affording a phenanthrene derivative and the Au(III) hydride complex (N^C^C)AuH. Steric shielding prevents intermolecular carbene trapping. The related (N^C^C)Au-C-SiMe<sub>3</sub> carbene <b>7</b> was generated and characterized by <i>in crystallo</i> photolysis. In solution, it displays intermolecular reactivity typical for triplet as well as singlet carbenes, such as H atom abstraction and carbene-type couplings with isocyanides. DFT calculations shed light on the structure, bonding, and reactivity of these Au(III)-substituted carbenes.
Authors
- Shuo Li (ORCID: https://orcid.org/0000-0001-9593-5367)
- Didier Bourissou
- Rui Wei
- Nina Albouy
- Karinne Miqueu
Institutions
- Centre National de la Recherche Scientifique (FR)
- Université de Pau et des Pays de l'Adour (FR)
- Université Fédérale de Toulouse Midi-Pyrénées (FR)
- Institut des Sciences Analytiques et de Physico-Chimie pour l'Environnement et les Matériaux (FR)
- Institut de Chimie de Strasbourg (FR)
- Institut de Chimie (FR)
- Laboratoire Hétérochimie Fondamentale et Appliquée (FR)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2026-01-26
- DOI
- https://doi.org/10.1021/jacs.5c17756
- Primary Topic
- Cyclopropane Reaction Mechanisms
- Type
- article
- Field-Weighted Citation Impact
- 0.00