C−H Activation by an Iron‐Nitrido Bis‐Pocket Porphyrin Species

Abstract

AbstractHigh‐valent iron‐nitrido species are nitrogen analogues of iron‐oxo species which are versatile reagents for C−H oxidation. Nonetheless, C−H activation by iron‐nitrido species has been scarcely explored, as this is often hampered by their instability and short lifetime in solutions. Herein, the hydrogen atom transfer (HAT) reactivity of an Fe porphyrin nitrido species (2 c) toward C−H substrates was studied in solutions at room temperature, which was achieved by nanosecond laser flash photolysis (LFP) of its FeIII‐azido precursor (1 c) supported by a bulky bis‐pocket porphyrin ligand. C−H bonds with bond dissociation enthalpies (BDEs) of up to ≈84 kcal mol−1 could be activated, and the second‐order rate constants (k2) are on the order of 102–104 s−1 m−1. The Fe‐amido product formed after HAT could further release ammonia upon protonation.