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Ligand‐Enabled Disproportionation of 1,2‐Diphenylhydrazine at a P(V)‐Center

We present herein the synthesis of a nearly square‐pyramidal chlorophosphorane supported by the tetradentate bis(amidophenolate) ligand, N,N′‐bis(3,5‐di‐tert‐butyl‐2‐phenoxy)‐1,2‐phenylenediamide. After chloride abstraction the resulting phosphonium cation efficiently promotes the disproportionation...

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Autores principales: Karnbrock, Simon B. H., Golz, Christopher, Mata, Ricardo A., Alcarazo, Manuel
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/PMC9542402/
https://www.ncbi.nlm.nih.gov/pubmed/35714171
http://dx.doi.org/10.1002/anie.202207450
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author Karnbrock, Simon B. H.
Golz, Christopher
Mata, Ricardo A.
Alcarazo, Manuel
author_facet Karnbrock, Simon B. H.
Golz, Christopher
Mata, Ricardo A.
Alcarazo, Manuel
author_sort Karnbrock, Simon B. H.
collection PubMed
description We present herein the synthesis of a nearly square‐pyramidal chlorophosphorane supported by the tetradentate bis(amidophenolate) ligand, N,N′‐bis(3,5‐di‐tert‐butyl‐2‐phenoxy)‐1,2‐phenylenediamide. After chloride abstraction the resulting phosphonium cation efficiently promotes the disproportionation of 1,2‐diphenylhydrazine to aniline and azobenzene. Mechanistic studies, spectroscopic analyses and theoretical calculations suggest that this unprecedented reactivity mode for P(V)‐centres is induced by the high electrophilicity at the cationic P(V)‐center, which originates from the geometry constraints imposed by the rigid pincer ligand, combined with the ability of the o‐amidophenolate moieties to act as electron reservoir. This study illustrates the promising role of cooperativity between redox‐active ligands and phosphorus for the design of organocatalysts able to promote redox processes.
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spelling pubmed-95424022022-10-14 Ligand‐Enabled Disproportionation of 1,2‐Diphenylhydrazine at a P(V)‐Center Karnbrock, Simon B. H. Golz, Christopher Mata, Ricardo A. Alcarazo, Manuel Angew Chem Int Ed Engl Research Articles We present herein the synthesis of a nearly square‐pyramidal chlorophosphorane supported by the tetradentate bis(amidophenolate) ligand, N,N′‐bis(3,5‐di‐tert‐butyl‐2‐phenoxy)‐1,2‐phenylenediamide. After chloride abstraction the resulting phosphonium cation efficiently promotes the disproportionation of 1,2‐diphenylhydrazine to aniline and azobenzene. Mechanistic studies, spectroscopic analyses and theoretical calculations suggest that this unprecedented reactivity mode for P(V)‐centres is induced by the high electrophilicity at the cationic P(V)‐center, which originates from the geometry constraints imposed by the rigid pincer ligand, combined with the ability of the o‐amidophenolate moieties to act as electron reservoir. This study illustrates the promising role of cooperativity between redox‐active ligands and phosphorus for the design of organocatalysts able to promote redox processes. John Wiley and Sons Inc. 2022-07-20 2022-08-26 /pmc/articles/PMC9542402/ /pubmed/35714171 http://dx.doi.org/10.1002/anie.202207450 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
Karnbrock, Simon B. H.
Golz, Christopher
Mata, Ricardo A.
Alcarazo, Manuel
Ligand‐Enabled Disproportionation of 1,2‐Diphenylhydrazine at a P(V)‐Center
title Ligand‐Enabled Disproportionation of 1,2‐Diphenylhydrazine at a P(V)‐Center
title_full Ligand‐Enabled Disproportionation of 1,2‐Diphenylhydrazine at a P(V)‐Center
title_fullStr Ligand‐Enabled Disproportionation of 1,2‐Diphenylhydrazine at a P(V)‐Center
title_full_unstemmed Ligand‐Enabled Disproportionation of 1,2‐Diphenylhydrazine at a P(V)‐Center
title_short Ligand‐Enabled Disproportionation of 1,2‐Diphenylhydrazine at a P(V)‐Center
title_sort ligand‐enabled disproportionation of 1,2‐diphenylhydrazine at a p(v)‐center
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9542402/
https://www.ncbi.nlm.nih.gov/pubmed/35714171
http://dx.doi.org/10.1002/anie.202207450
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