Electrocatalytic Azide Oxidation Mediated by a Rh(PNP) Pincer Complex

One‐electron oxidation of the rhodium(I) azido complex [Rh(N(3))(PNP)] (5), bearing the neutral, pyridine‐based PNP ligand 2,6‐bis(di‐tert‐butylphosphinomethyl)pyridine, leads to instantaneous and selective formation of the mononuclear rhodium(I) dinitrogen complex [Rh(N(2))(PNP)](+) (9 (+)). Intere...

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Autores principales: Rebreyend, Christophe, Gloaguen, Yann, Lutz, Martin, van der Vlugt, Jarl Ivar, Siewert, Inke, Schneider, Sven, de Bruin, Bas
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2017
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5765409/
https://www.ncbi.nlm.nih.gov/pubmed/28898478
http://dx.doi.org/10.1002/chem.201702938
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author Rebreyend, Christophe
Gloaguen, Yann
Lutz, Martin
van der Vlugt, Jarl Ivar
Siewert, Inke
Schneider, Sven
de Bruin, Bas
author_facet Rebreyend, Christophe
Gloaguen, Yann
Lutz, Martin
van der Vlugt, Jarl Ivar
Siewert, Inke
Schneider, Sven
de Bruin, Bas
author_sort Rebreyend, Christophe
collection PubMed
description One‐electron oxidation of the rhodium(I) azido complex [Rh(N(3))(PNP)] (5), bearing the neutral, pyridine‐based PNP ligand 2,6‐bis(di‐tert‐butylphosphinomethyl)pyridine, leads to instantaneous and selective formation of the mononuclear rhodium(I) dinitrogen complex [Rh(N(2))(PNP)](+) (9 (+)). Interestingly, complex 5 also acts as a catalyst for electrochemical N(3) (−) oxidation (E (p)≈−0.23 V vs. Fc(+/0)) in the presence of excess azide. This is of potential relevance for the design of azide‐based and direct ammonia fuel cells, expelling only harmless dinitrogen as an exhaust gas.
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spelling pubmed-57654092018-02-01 Electrocatalytic Azide Oxidation Mediated by a Rh(PNP) Pincer Complex Rebreyend, Christophe Gloaguen, Yann Lutz, Martin van der Vlugt, Jarl Ivar Siewert, Inke Schneider, Sven de Bruin, Bas Chemistry Communications One‐electron oxidation of the rhodium(I) azido complex [Rh(N(3))(PNP)] (5), bearing the neutral, pyridine‐based PNP ligand 2,6‐bis(di‐tert‐butylphosphinomethyl)pyridine, leads to instantaneous and selective formation of the mononuclear rhodium(I) dinitrogen complex [Rh(N(2))(PNP)](+) (9 (+)). Interestingly, complex 5 also acts as a catalyst for electrochemical N(3) (−) oxidation (E (p)≈−0.23 V vs. Fc(+/0)) in the presence of excess azide. This is of potential relevance for the design of azide‐based and direct ammonia fuel cells, expelling only harmless dinitrogen as an exhaust gas. John Wiley and Sons Inc. 2017-10-12 2017-12-11 /pmc/articles/PMC5765409/ /pubmed/28898478 http://dx.doi.org/10.1002/chem.201702938 Text en © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution‐NonCommercial (http://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 Communications
Rebreyend, Christophe
Gloaguen, Yann
Lutz, Martin
van der Vlugt, Jarl Ivar
Siewert, Inke
Schneider, Sven
de Bruin, Bas
Electrocatalytic Azide Oxidation Mediated by a Rh(PNP) Pincer Complex
title Electrocatalytic Azide Oxidation Mediated by a Rh(PNP) Pincer Complex
title_full Electrocatalytic Azide Oxidation Mediated by a Rh(PNP) Pincer Complex
title_fullStr Electrocatalytic Azide Oxidation Mediated by a Rh(PNP) Pincer Complex
title_full_unstemmed Electrocatalytic Azide Oxidation Mediated by a Rh(PNP) Pincer Complex
title_short Electrocatalytic Azide Oxidation Mediated by a Rh(PNP) Pincer Complex
title_sort electrocatalytic azide oxidation mediated by a rh(pnp) pincer complex
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5765409/
https://www.ncbi.nlm.nih.gov/pubmed/28898478
http://dx.doi.org/10.1002/chem.201702938
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