Transient terminal Cu-nitrene intermediates from discrete dicopper nitrenes

Area of Science:

• Organometallic Chemistry
• Inorganic Chemistry
• Coordination Chemistry

Background:

• Copper(I) complexes with beta-diketiminate ligands are valuable in synthetic chemistry.
• Aryl azides are versatile precursors for nitrogen-containing compounds.
• Dicopper nitrenes are reactive intermediates with potential applications.

Purpose of the Study:

• To synthesize and characterize a novel dicopper nitrene complex.
• To investigate the reactivity of the dicopper nitrene with other copper complexes and small molecules.
• To explore the structural and electronic properties of dicopper nitrene species.

Main Methods:

• Synthesis of copper(I) beta-diketiminate and aryl azide.
• Characterization of the dicopper nitrene using X-ray crystallography.
• Reaction studies with copper(I) anilidoimine and phosphine/isocyanide ligands.
• Spectroscopic analysis of reaction products.

Main Results:

• Formation of the dicopper nitrene {[Me3NN]Cu}2(mu-NAr) in 77% yield.
• X-ray structure reveals a nearly symmetric dicopper nitrene with specific Cu-N bond distances and Cu-N-Cu angle.
• Reaction with Cu(I) anilidoimine yields new unsymmetrical and symmetrical dicopper nitrenes.
• Dicopper nitrene exhibits electrophilic reactivity, reacting with PMe3 and CNtBu to form phosphazenes and carbodiimides, respectively.
• Isolation and structural characterization of a Cu(I) phosphaimide complex.

Conclusions:

• The study successfully synthesized and characterized a novel dicopper nitrene.
• The dicopper nitrene exhibits dynamic behavior and reactivity towards copper complexes and small molecules.
• The findings provide insights into the chemistry of dicopper nitrenes and their potential as synthetic intermediates.