Bypassing the Nitrido Wall Using a Redox-Active Isocyanide: Nucleophilic Attack on CO by a Rhenium Nitride Complex

Area of Science:

• Inorganic Chemistry
• Organometallic Chemistry
• Materials Science

Background:

• Reactive rhenium(III) nitride complexes are typically unstable and rare due to the
• nitrido wall" phenomenon.
• Filling Re─N π* orbitals is theoretically possible but challenging to achieve experimentally.
• Existing methods struggle to access stable and reactive nitride species.

Purpose of the Study:

• To develop a novel strategy for synthesizing stable and reactive rhenium nitride complexes.
• To bypass the limitations imposed by the "nitrido wall" in nitride chemistry.
• To demonstrate the utility of these complexes in N─C bond formation.

Main Methods:

• Incorporation of a redox-active isocyanide supporting ligand.
• Crystallographic, spectroscopic, and computational studies to characterize the complex.
• Reaction of the rhenium nitride complex with carbon monoxide (CO).

Main Results:

• A method to bypass the "nitrido wall" was successfully developed.
• The redox-active isocyanide ligand accommodated two electrons, stabilizing the nitride.
• The rhenium nitride complex readily reacted with CO to form a cyanate complex, showcasing nucleophilic reactivity.
• Demonstrated N─C bond forming reactivity using an N₂-derived rhenium nitride.

Conclusions:

• The use of a redox-active isocyanide ligand is a viable strategy to stabilize reactive rhenium nitrides.
• This approach overcomes the "nitrido wall" and enables access to unprecedented nitride reactivity.
• The developed method opens new avenues for nitrogen fixation and C─N bond formation in organometallic chemistry.