Nitrosonium Reactivity of (NHC)Copper(I) Sulfide Complexes

Area of Science:

• Organometallic Chemistry
• Coordination Chemistry
• Sulfur Chemistry

Background:

• N-heterocyclic carbenes (NHCs) are versatile ligands in organometallic chemistry.
• Copper sulfide complexes are relevant in catalysis and materials science.
• Understanding the reactivity of copper-sulfur bonds is crucial for synthetic applications.

Purpose of the Study:

• To investigate the reactivity of copper(I) sulfide complexes supported by an expanded-ring NHC (7Dipp) ligand.
• To elucidate the reaction pathways of these complexes with the nitrosonium ion (NO+).
• To characterize the products formed, including elemental sulfur and various copper species.

Main Methods:

• Synthesis of copper(I) sulfide, disulfide, and hydrosulfide complexes stabilized by the 7Dipp ligand.
• Reaction of these complexes with the nitrosonium ion (NO+).
• Characterization of reaction products using spectroscopic and analytical techniques.

Main Results:

• 7Dipp ligand supports neutral sulfide- and disulfide-bridged dicopper(I) complexes and mononuclear copper(I) hydrosulfide.
• Reaction with NO+ leads to NHC-supported copper(I) cations and elemental sulfur.
• Dicopper(I) sulfide/disulfide complexes reduce to copper(0), while copper(I) hydrosulfide and hydride complexes form ammonium ions.

Conclusions:

• The expanded-ring NHC ligand (7Dipp) effectively stabilizes various copper(I) sulfur species.
• The nitrosonium ion (NO+) serves as a reactive probe, differentiating the reactivity of copper-sulfur complexes.
• The study highlights distinct reaction pathways for copper(I) sulfide, hydrosulfide, and hydride complexes with NO+.