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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...
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/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. |
format | Online Article Text |
id | pubmed-9542402 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
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
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title_full | Ligand‐Enabled Disproportionation of 1,2‐Diphenylhydrazine at a P(V)‐Center
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title_fullStr | Ligand‐Enabled Disproportionation of 1,2‐Diphenylhydrazine at a P(V)‐Center
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title_full_unstemmed | Ligand‐Enabled Disproportionation of 1,2‐Diphenylhydrazine at a P(V)‐Center
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title_short | Ligand‐Enabled Disproportionation of 1,2‐Diphenylhydrazine at a P(V)‐Center
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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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