Gold(III)-Substituted Carbenes

Area of Science:

• Organometallic Chemistry
• Photochemistry
• Carbene Chemistry

Background:

• Gold complexes are valuable in catalysis and synthesis.
• Diazo compounds are versatile precursors for carbene generation.
• Understanding gold carbene reactivity is crucial for developing new synthetic methodologies.

Purpose of the Study:

• To synthesize and characterize novel Au(III)-substituted diazo compounds.
• To investigate the photochemical extrusion of dinitrogen from these compounds.
• To explore the reactivity of the generated Au(III) carbenes.

Main Methods:

• Synthesis of (N^C^C)Au-diazo precursors.
• UV-vis irradiation for dinitrogen extrusion.
• Characterization of intermediates and products using spectroscopic methods.
• Density Functional Theory (DFT) calculations.

Main Results:

• Successful synthesis of Au(III)-substituted diazo compounds.
• Photolytic dinitrogen extrusion yielding Au(III) carbenes.
• Observation of intramolecular C-H insertion and β-H elimination for an Au-Dmp carbene.
• Characterization of an Au-SiMe3 carbene via in crystallo photolysis.
• Demonstration of intermolecular reactivity (H-abstraction, coupling) for the Au-SiMe3 carbene in solution.

Conclusions:

• Au(III)-substituted diazo compounds are viable precursors for Au(III) carbenes.
• The reactivity of Au(III) carbenes is influenced by the substituents.
• Steric hindrance plays a role in directing carbene reaction pathways.
• DFT calculations provide valuable insights into the electronic structure and reactivity of these species.