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

Abstract

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 <i>λ</i> = 457 nm and reductive quenching by NEt₃. 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 <i>vs.</i> 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.