Redox and photocatalytic properties of a Ni(II) complex with a macrocyclic biquinazoline (Mabiq) ligand

We present a late, first row transition metal photosensitizer that promotes photocatalytic C–C bond formation. The title compound, [Ni(Mabiq)]OTf, as well as its one-electron reduced form, Ni(Mabiq), were synthesized and molecular structures of both were obtained. The electronic structure of the reduced complex additionally was characterized by spectroscopic and DFT computational methods. Notably, [Ni(II)(Mabiq)]OTf is photoactive: reduction of the compound was achieved photochemically upon irradiation at λ = 457 nm and reductive quenching by NEt(3). The performance of [Ni(Mabiq)]OTf as a photoredox catalyst was examined in the cyclization of a bromoalkyl-substituted indole. In this reaction, the first-row transition metal compound is comparable if not superior to [Ru(bpy)(3)](2+) in terms of efficiency (turnover number) and chemoselectivity. Studies using a series of sacrificial donor amines indicate that the excited state redox potential of [Ni(Mabiq)](+)* is ≥1.25 V vs. SCE. This value is similar to the excited state potential of commonly employed noble metal based photocatalysts. The Ni-Mabiq compound thus provides a rare example of an earth-abundant photoredox catalyst.