Gold(III)-Substituted Carbenes
Abstract
The Au(III)-substituted diazo compounds (N^C^C)AuC(N 2 )R (R = Dmp = 2,6-dimesitylphenyl and SiMe 3 ) 1 and 6 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 3 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 3 carbene 7 was generated and characterized by in crystallo 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.
Fields of Study & Subjects
Cyclopropane Reaction Mechanisms
Catalytic Alkyne Reactions
Organometallic Complex Synthesis and Catalysis
Publication details
- Journal / source
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Volume
- 148
- Issue
- 4
- Pages
- 4295–4304
- Publication date
- 26 January 2026
- Language
- EN