An Open-Shell FeIV Nitrido
We report the photogeneration and characterization of an open-shell, terminal iron nitrido (EmL)Fe(N) using a sterically encumbered dipyrrin ligand environment. The Fe–N distance in the solid-state, zero-field 57Fe Mössbauer spectrum, and computational analysis are consistent with a triplet electronic ground state of the iron nitrido. Notably, the attenuation of Fe–N multiple bond character through occupying π*Fe–N enables (i) primary C(sp3)–H amination, (ii) H2 cleavage, (iii) aromatic C–C cleavage, and (iv) photocatalytic N-atom transfer reactivity. These modes of reactivity have not previously been observed in low-spin Fe(N) analogues.
