Leveraging ligand-based proton and electron transfer for aerobic reactivity and catalysis

Abstract

While O2 is an abundant, benign, and thermodynamically potent oxidant, it is also kinetically inert. This frequently limits its use in synthetic transformations. Correspondingly, direct aerobic reactivity with O2 often requires comparatively harsh or forcing conditions to overcome this kinetic barrier. Forcing conditions limit product selectivity and can lead to over oxidation. Alternatively, O2 can be activated by a catalyst to facilitate oxidative reactivity, and there are a variety of sophisticated examples where transition metal catalysts facilitate aerobic reactivity. Many efforts have focused on using metal–ligand cooperativity to facilitate the movement of protons and electrons for O2 activation. This approach is inspired by enzyme active sites, which frequently use the secondary sphere to facilitate both the activation of O2 and the oxidation of substrates. However, there has only recently been a focus on harnessing metal–ligand cooperativity for aerobic reactivity and, especially, catalysis. This perspective will discuss recent efforts to channel metal–ligand cooperativity for the activation of O2, the generation and stabilization of reactive metal–oxygen intermediates, and oxidative reactivity and catalysis. While significant progress has been made in this area, there are still challenges to overcome and opportunities for the development of efficient catalysts which leverage this biomimetic strategy.

Graphical abstract: Leveraging ligand-based proton and electron transfer for aerobic reactivity and catalysis

Article information

Article type
Perspective
Submitted
13 Jun 2024
Accepted
08 Sep 2024
First published
09 Sep 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2024, Advance Article

Leveraging ligand-based proton and electron transfer for aerobic reactivity and catalysis

K. A. Jesse and J. S. Anderson, Chem. Sci., 2024, Advance Article , DOI: 10.1039/D4SC03896G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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