Cargando…

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...

Descripción completa

Detalles Bibliográficos
Autores principales: Fritz, Maximilian, Rupp, Severine, Kiene, Ciara I., Kisan, Sesha, Telser, Joshua, Würtele, Christian, Krewald, Vera, Schneider, Sven
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
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
_version_ 1784804070934970368
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
work_keys_str_mv AT fritzmaximilian photoelectrochemicalconversionofdinitrogentobenzonitrileselectivitycontrolbyelectrophileversusprotoncoupledelectrontransfer
AT ruppseverine photoelectrochemicalconversionofdinitrogentobenzonitrileselectivitycontrolbyelectrophileversusprotoncoupledelectrontransfer
AT kieneciarai photoelectrochemicalconversionofdinitrogentobenzonitrileselectivitycontrolbyelectrophileversusprotoncoupledelectrontransfer
AT kisansesha photoelectrochemicalconversionofdinitrogentobenzonitrileselectivitycontrolbyelectrophileversusprotoncoupledelectrontransfer
AT telserjoshua photoelectrochemicalconversionofdinitrogentobenzonitrileselectivitycontrolbyelectrophileversusprotoncoupledelectrontransfer
AT wurtelechristian photoelectrochemicalconversionofdinitrogentobenzonitrileselectivitycontrolbyelectrophileversusprotoncoupledelectrontransfer
AT krewaldvera photoelectrochemicalconversionofdinitrogentobenzonitrileselectivitycontrolbyelectrophileversusprotoncoupledelectrontransfer
AT schneidersven photoelectrochemicalconversionofdinitrogentobenzonitrileselectivitycontrolbyelectrophileversusprotoncoupledelectrontransfer