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  • Title: Long-Lived Charge-Transfer States of Nickel(II) Aryl Halide Complexes Facilitate Bimolecular Photoinduced Electron Transfer.
    Author: Shields BJ, Kudisch B, Scholes GD, Doyle AG.
    Journal: J Am Chem Soc; 2018 Feb 28; 140(8):3035-3039. PubMed ID: 29400956.
    Abstract:
    Here we investigate the photophysics and photochemistry of Ni(II) aryl halide complexes common to cross-coupling and Ni/photoredox reactions. Computational and ultrafast spectroscopic studies reveal that these complexes feature long-lived 3MLCT excited states, implicating Ni as an underexplored alternative to precious metal photocatalysts. Moreover, we show that 3MLCT Ni(II) engages in bimolecular electron transfer with ground-state Ni(II), which enables access to Ni(III) in the absence of external oxidants or photoredox catalysts. As such, it is possible to facilitate Ni-catalyzed C-O bond formation solely by visible light irradiation, thus representing an alternative strategy for catalyst activation in Ni cross-coupling reactions.
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