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Photoelectrochemical Conversion of Dinitrogen to Benzonitrile: Selectivity Control by Electrophile‐ versus Proton‐Coupled Electron Transfer
Nitride complexes are key species in homogeneous nitrogen fixation to NH(3) via stepwise proton‐coupled electron transfer (PCET). In contrast, direct generation of nitrogenous organic products from N(2)‐derived nitrides requires new strategies to enable efficient reductive nitride transfer in the pr...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9542086/ https://www.ncbi.nlm.nih.gov/pubmed/35714100 http://dx.doi.org/10.1002/anie.202205922 |
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author | Fritz, Maximilian Rupp, Severine Kiene, Ciara I. Kisan, Sesha Telser, Joshua Würtele, Christian Krewald, Vera Schneider, Sven |
author_facet | Fritz, Maximilian Rupp, Severine Kiene, Ciara I. Kisan, Sesha Telser, Joshua Würtele, Christian Krewald, Vera Schneider, Sven |
author_sort | Fritz, Maximilian |
collection | PubMed |
description | Nitride complexes are key species in homogeneous nitrogen fixation to NH(3) via stepwise proton‐coupled electron transfer (PCET). In contrast, direct generation of nitrogenous organic products from N(2)‐derived nitrides requires new strategies to enable efficient reductive nitride transfer in the presence of organic electrophiles. We here present a 2‐step protocol for the conversion of dinitrogen to benzonitrile. Photoelectrochemical, reductive N(2) splitting produces a rhenium(V) nitride with unfavorable PCET thermochemistry towards ammonia generation. However, N‐benzoylation stabilizes subsequent reduction as a basis for selective nitrogen transfer in the presence of the organic electrophile and Brønsted acid at mild reduction potentials. This work offers a new strategy for photoelectrosynthetic nitrogen fixation beyond ammonia—to yield nitrogenous organic products. |
format | Online Article Text |
id | pubmed-9542086 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-95420862022-10-14 Photoelectrochemical Conversion of Dinitrogen to Benzonitrile: Selectivity Control by Electrophile‐ versus Proton‐Coupled Electron Transfer Fritz, Maximilian Rupp, Severine Kiene, Ciara I. Kisan, Sesha Telser, Joshua Würtele, Christian Krewald, Vera Schneider, Sven Angew Chem Int Ed Engl Research Articles Nitride complexes are key species in homogeneous nitrogen fixation to NH(3) via stepwise proton‐coupled electron transfer (PCET). In contrast, direct generation of nitrogenous organic products from N(2)‐derived nitrides requires new strategies to enable efficient reductive nitride transfer in the presence of organic electrophiles. We here present a 2‐step protocol for the conversion of dinitrogen to benzonitrile. Photoelectrochemical, reductive N(2) splitting produces a rhenium(V) nitride with unfavorable PCET thermochemistry towards ammonia generation. However, N‐benzoylation stabilizes subsequent reduction as a basis for selective nitrogen transfer in the presence of the organic electrophile and Brønsted acid at mild reduction potentials. This work offers a new strategy for photoelectrosynthetic nitrogen fixation beyond ammonia—to yield nitrogenous organic products. John Wiley and Sons Inc. 2022-07-18 2022-08-26 /pmc/articles/PMC9542086/ /pubmed/35714100 http://dx.doi.org/10.1002/anie.202205922 Text en © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc/4.0/ (https://creativecommons.org/licenses/by-nc/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes. |
spellingShingle | Research Articles Fritz, Maximilian Rupp, Severine Kiene, Ciara I. Kisan, Sesha Telser, Joshua Würtele, Christian Krewald, Vera Schneider, Sven Photoelectrochemical Conversion of Dinitrogen to Benzonitrile: Selectivity Control by Electrophile‐ versus Proton‐Coupled Electron Transfer |
title | Photoelectrochemical Conversion of Dinitrogen to Benzonitrile: Selectivity Control by Electrophile‐ versus Proton‐Coupled Electron Transfer |
title_full | Photoelectrochemical Conversion of Dinitrogen to Benzonitrile: Selectivity Control by Electrophile‐ versus Proton‐Coupled Electron Transfer |
title_fullStr | Photoelectrochemical Conversion of Dinitrogen to Benzonitrile: Selectivity Control by Electrophile‐ versus Proton‐Coupled Electron Transfer |
title_full_unstemmed | Photoelectrochemical Conversion of Dinitrogen to Benzonitrile: Selectivity Control by Electrophile‐ versus Proton‐Coupled Electron Transfer |
title_short | Photoelectrochemical Conversion of Dinitrogen to Benzonitrile: Selectivity Control by Electrophile‐ versus Proton‐Coupled Electron Transfer |
title_sort | photoelectrochemical conversion of dinitrogen to benzonitrile: selectivity control by electrophile‐ versus proton‐coupled electron transfer |
topic | Research Articles |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9542086/ https://www.ncbi.nlm.nih.gov/pubmed/35714100 http://dx.doi.org/10.1002/anie.202205922 |
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