Redox Non‐Innocent Behavior of a Terminal Iridium Hydrazido(2−) Triple Bond

Abstract The synthesis of the first terminal Group 9 hydrazido(2‐) complex, Cp*IrN(TMP) ( 6 ) (TMP=2,2,6,6‐tetramethylpiperidine) is reported. Electronic structure and X‐ray diffraction analysis indicate that this complex contains an Ir−N triple bond, similar to Bergman's seminal Cp*Ir(N t Bu) imido complex. However, in sharp contrast to Bergman's imido, 6 displays remarkable redox non‐innocent reactivity owing to the presence of the N β lone pair. Treatment of 6 with MeI results in electron transfer from N β to Ir prior to oxidative addition of MeI to the iridium center. This behavior opens the possibility of carrying out facile oxidative reactions at a formally Ir III metal center through a hydrazido(2−)/isodiazene valence tautomerization.