An iridium(III/IV/V) redox series featuring a terminal imido complex with triplet ground state

The iridium(III/IV/V) imido redox series [Ir(NtBu){N(CHCHPtBu₂)₂}]^0/+/2+ was synthesized and examined spectroscopically, magnetically, crystallographically and computationally. The monocationic iridium(IV) imide exhibits an electronic doublet ground state with considerable ‘imidyl’ character as a result of covalent Ir–NtBu bonding. Reduction gives the neutral imide [Ir(NtBu){N(CHCHPtBu₂)₂}] as the first example of an iridium complex with a triplet ground state. Its reactivity with respect to nitrene transfer to selected electrophiles (CO₂) and nucleophiles (PMe₃), respectively, is reported.