Transient Absorption Spectroscopy Offers Mechanistic Insights for an Iridium/Nickel-Catalyzed C–O Coupling
2020
Tian, Lei | Till, Nicholas A. | Kudisch, Bryan | MacMillan, David W. C. | Scholes, Gregory D.
We report mechanistic insights into an iridium/nickel photocatalytic C–O cross-coupling reaction from time-resolved spectroscopic studies. Using transient absorption spectroscopy, energy transfer from an iridium photocatalyst to a catalytically relevant Ni(II)(aryl) acetate acceptor was observed. Concentration-dependent lifetime measurements suggest the mechanism of the subsequent reductive elimination is a unimolecular process occurring on the long-lived excited state of the Ni(II) complex. We envision that our study of the productive energy-transfer-mediated pathway would encourage the development of new excited-state reactivities in the field of metallaphotocatalysis that are enabled by light harvesting.
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