An Open-Shell Fe Nitrido.

We report the photogeneration and characterization of an open-shell, terminal iron nitrido (L)Fe(N) using a sterically encumbered dipyrrin ligand environment. The Fe-N distance in the solid-state, zero-field Fe 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* enables (i) primary C(sp)-H amination, (ii) H cleavage, (iii) aromatic C-C cleavage, and (iv) photocatalytic -atom transfer reactivity. These modes of reactivity have not previously been observed in low-spin Fe(N) analogues.