Discovery of a Photoinduced Dark Catalytic Cycle Using in Situ LED-NMR Spectroscopy

Journal of the American Chemical Society
Dan LehnherrMikhail Reibarkh

Abstract

We report the use of LED-NMR spectroscopy to study the reaction mechanism of a newly discovered photoinduced iron-catalyzed cycloisomerization of alkynols to cyclic enol ethers. By understanding on/off ligand binding to the catalyst, we were able to appropriately design reaction conditions to balance catalyst activity and stability. LED-NMR was demonstrated to be a powerful tool in elucidating reaction mechanisms of photochemical reactions. Temporal NMR spectroscopic data under visible light illumination (1) revealed the pre-catalyst activation mechanism, (2) proved that photon flux provides a unique external control of the equilibrium distribution between the pre-catalyst and active catalyst, and ultimately the rate of reaction, (3) provided information about the reaction driving forces and the turnover-limiting step, and (4) enabled both real-time structural and kinetic insights into elusive species (e.g., dissolved gases).

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Citations

Feb 7, 2020·Chemistry : a European Journal·Enrico BergamaschiChristopher J Teskey
Jul 3, 2020·Chemistry : a European Journal·Wen-Jun ZhouDa-Gang Yu
Oct 28, 2019·Inorganic Chemistry·Thomas J FeuersteinPeter W Roesky
May 30, 2020·Journal of the American Chemical Society·Jamal A MalikPeter H Seeberger
Jun 15, 2019·Accounts of Chemical Research·Erik L RegaladoDavy Guillarme
Sep 25, 2021·Chemical Reviews·Lisa CandishSebastian Keess

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