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(NtBu) imido complex. However in sharp contrast to Bergman’s imido, 6 displays remarkable redox noninnocent reactivity owing to the presence of the Nβ lone pair. Treatment of 6 with MeI results in electron transfer from Nβ 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 IrIII metal center via a hydrazido(2−)/isodiazene valence tautomerization.

The synthesis of the first terminal Group 9 hydrazido(2-) complex, Cp*IrN(TMP) (6)( TMP = 2,2,6,6tetramethylpiperidine) is reported. Electronic structure and Xray diffraction analysis indicate that this complex contains an IrÀNt riple bond, similar to Bergmanss eminal Cp*Ir(N t Bu) imido complex. However,i ns harp contrast to Bergmans imido, 6 displays remarkable redoxn on-innocent reactivity owingtothe presence of the N b lone pair.T reatment of 6 with MeI results in electron transfer from N b to Ir prior to oxidative addition of MeI to the iridium center.This behavior opens the possibility of carrying out facile oxidative reactions at af ormally Ir III metal center through ah ydrazido(2À)/isodiazene valence tautomerization.