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Photochemistry of the pyruvate anion produces CO2, CO, CH3–, CH3, and a low energy electron

Clarke, Connor J. and Gibbard, Jemma A. and Hutton, Lewis and Verlet, Jan R. R. and Curchod, Basile F. E. (2022) 'Photochemistry of the pyruvate anion produces CO2, CO, CH3–, CH3, and a low energy electron.', Nature communications., 13 (1). p. 937.

Abstract

The photochemistry of pyruvic acid has attracted much scientific interest because it is believed to play critical roles in atmospheric chemistry. However, under most atmospherically relevant conditions, pyruvic acid deprotonates to form its conjugate base, the photochemistry of which is essentially unknown. Here, we present a detailed study of the photochemistry of the isolated pyruvate anion and uncover that it is extremely rich. Using photoelectron imaging and computational chemistry, we show that photoexcitation by UVA light leads to the formation of CO2, CO, and CH3−. The observation of the unusual methide anion formation and its subsequent decomposition into methyl radical and a free electron may hold important consequences for atmospheric chemistry. From a mechanistic perspective, the initial decarboxylation of pyruvate necessarily differs from that in pyruvic acid, due to the missing proton in the anion.

Item Type:Article
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Status:Peer-reviewed
Publisher Web site:https://doi.org/10.1038/s41467-022-28582-4
Publisher statement:Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
Date accepted:01 February 2022
Date deposited:16 March 2022
Date of first online publication:17 February 2022
Date first made open access:16 March 2022

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