Nitrene Radical Intermediates in Catalytic Synthesis

Nitrene radical complexes are reactive intermediates with discrete spin density at the nitrogen‐atom of the nitrene moiety. These species have become important intermediates for organic synthesis, being invoked in a broad range of C−H functionalization and aziridination reactions. Nitrene radical complexes have intriguing electronic structures, and are best described as one‐electron reduced Fischer type nitrenes. They can be generated by intramolecular single electron transfer to the “redox non‐innocent” nitrene moiety at the metal. Nitrene radicals generated at open‐shell cobalt(II) have thus far received most attention in terms of spectroscopic characterization, reactivity screening, catalytic nitrene‐transfer reactions and (computational and experimental) mechanistic studies, but some interesting iron and precious metal catalysts have also been employed in related reactions involving nitrene radicals. In some cases, redox‐active ligands are used to facilitate intramolecular single electron transfer from the complex to the nitrene moiety. Organic azides are among the most attractive nitrene precursors in this field, typically requiring pre‐activated organic azides (e.g. RSO(2)N(3), (RO)(2)P(=O)N(3), ROC(=O)N(3) and alike) to achieve efficient and selective catalysis. Challenging, non‐activated aliphatic organic azides were recently added to the palette of reagents useful in synthetically relevant reactions proceeding via nitrene radical intermediates. This concept article describes the electronic structure of nitrene radical complexes, emphasizes on their usefulness in the catalytic synthesis of various organic products, and highlights the important developments in the field.