A low-coordinate iron organoazide complex.

Area of Science:

• Organometallic Chemistry
• Coordination Chemistry
• Iron Complexes

Background:

• Organoazide complexes are valuable precursors in synthetic chemistry.
• Understanding the reactivity of labile azide ligands is crucial for developing new catalytic processes.

Purpose of the Study:

• To synthesize and characterize a novel labile organoazide iron complex.
• To investigate the reactivity of the azide ligand under various conditions, including thermal and photochemical activation.
• To elucidate the structure and electronic properties of reaction intermediates.

Main Methods:

• Synthesis and characterization of the organoazide iron complex.
• Solution-phase studies to determine dissociation equilibrium and reactivity.
• Single-crystal X-ray diffraction and low-temperature irradiation (80 K).
• Computational modeling (Density Functional Theory) to identify intermediates.

Main Results:

• A labile organoazide iron complex was successfully synthesized.
• The complex exhibits a dissociation equilibrium in solution and undergoes intramolecular C-H bond amination.
• Photochemical irradiation at 80 K leads to nitrogen extrusion and formation of a putative imido iron intermediate.
• Computational analysis identified the intermediate as a highly covalent {FeNR}⁸ species.

Conclusions:

• The reported organoazide iron complex is a versatile precursor with tunable reactivity.
• The formation and computational identification of the imido iron intermediate provide insights into nitrogen extrusion mechanisms.
• This work opens avenues for developing new iron-catalyzed amination reactions.