Exploiting the Marcus Inverted Region for First-row Transition Metal-based Photoredox Catalysis

Overview

Journal Science

Specialty Science

Date 2023 Oct 12

PMID 37824651

Authors

Amy Y Chan

Atanu Ghosh

Jonathan T Yarranton

Jack Twilton

Jian Jin

Daniela M Arias-Rotondo

Holt A Sakai

James K McCusker

David W C MacMillan

Affiliations

Soon will be listed here.

Abstract

Second- and third-row transition metal complexes are widely employed in photocatalysis, whereas earth-abundant first-row transition metals have found only limited use because of the prohibitively fast decay of their excited states. We report an unforeseen reactivity mode for productive photocatalysis that uses cobalt polypyridyl complexes as photocatalysts by exploiting Marcus inverted region behavior that couples increases in excited-state energies with increased excited-state lifetimes. These cobalt (III) complexes can engage in bimolecular reactivity by virtue of their strong redox potentials and sufficiently long excited-state lifetimes, catalyzing oxidative C(sp)-N coupling of aryl amides with challenging sterically hindered aryl boronic acids. More generally, the results imply that chromophores can be designed to increase excited-state lifetimes while simultaneously increasing excited-state energies, providing a pathway for the use of relatively abundant metals as photoredox catalysts.

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