Intramolecular C-H Functionalization Followed by a [2_σ + 2_π] Addition via an Intermediate Nickel-Nitridyl Complex

Irradiation of a disphenoidal Ni(II) azido complex, [Cz ^tBu(Pyr ^iPr)₂NiN₃] (1), revealed an unprecedented nickel complex, [Cz ^tBu(Pyr ^iPr)(NH₂-Pyr ^iPr)] (2), in >90% isolated yield. As evidenced by single-crystal X-ray diffraction, 2 is produced by double intramolecular C-H activation of a putative nickel-nitridyl intermediate, [Cz ^tBu(Pyr ^iPr)₂Ni-⃛N^•]. Calculations support the generation of an intermediate with significant nitridyl radical character after the loss of N₂, which, in turn, undergoes tandem C-H activations, leading to functionalized intermediates and products. This is an unprecedented example of transient Ni-⃛N^•-promoted intramolecular C-H functionalization, followed by a [2_σ + 2_π] addition, yielding bis-metallacyclic product 2. Complex 2 is also observed from the reaction of Ni(I) precursor Cz ^tBu(Pyr ^iPr)₂Ni (3) and Me₃SiN₃, suggesting a unique thermal route toward a masked nickel-nitridyl intermediate.