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Transient Phosphenium and Arsenium Ions versus Stable Stibenium and Bismuthenium Ions
Fluoride abstraction from bis‐m‐terphenylelement fluorides (2,6‐Mes(2)C(6)H(3))(2)EF (E=P, As) generated the highly reactive phosphenium ion [(2,6‐Mes(2)C(6)H(3))(2)P](+) and the arsenium ion [(2,6‐Mes(2)C(6)H(3))(2)As](+), which immediately underwent intramolecular electrophilic substitution and fo...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6900177/ https://www.ncbi.nlm.nih.gov/pubmed/31404472 http://dx.doi.org/10.1002/chem.201902520 |
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author | Olaru, Marian Duvinage, Daniel Lork, Enno Mebs, Stefan Beckmann, Jens |
author_facet | Olaru, Marian Duvinage, Daniel Lork, Enno Mebs, Stefan Beckmann, Jens |
author_sort | Olaru, Marian |
collection | PubMed |
description | Fluoride abstraction from bis‐m‐terphenylelement fluorides (2,6‐Mes(2)C(6)H(3))(2)EF (E=P, As) generated the highly reactive phosphenium ion [(2,6‐Mes(2)C(6)H(3))(2)P](+) and the arsenium ion [(2,6‐Mes(2)C(6)H(3))(2)As](+), which immediately underwent intramolecular electrophilic substitution and formation of an 1,2,4‐trimethyl‐6‐mesityl‐5‐m‐terphenyl‐benzo[b]phospholium ion and an 1,2,4‐trimethyl‐6‐mesityl‐5‐m‐terphenyl‐benzo[b]arsolium ion, respectively. The formation of the latter involved a methyl group migration from the ortho‐position of a flanking mesityl group to the meta‐position. This reactivity of [(2,6‐Mes(2)C(6)H(3))(2)E](+) (E=P, As) is in sharp contrast to the related stibenium ion [(2,6‐Mes(2)C(6)H(3))(2)Sb](+) and bismuthenium ion [(2,6‐Mes(2)C(6)H(3))(2)Bi](+), which have been recently isolated and fully characterized (Angew. Chem. Int. Ed. 2018, 57, 10080–10084). On the basis of DFT calculations, a mechanism for the rearrangement of the phosphenium and arsenium ions into the phospholium and arsolium ions is proposed, which is not feasible for the stibenium and bismuthenium ions. |
format | Online Article Text |
id | pubmed-6900177 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-69001772019-12-20 Transient Phosphenium and Arsenium Ions versus Stable Stibenium and Bismuthenium Ions Olaru, Marian Duvinage, Daniel Lork, Enno Mebs, Stefan Beckmann, Jens Chemistry Communications Fluoride abstraction from bis‐m‐terphenylelement fluorides (2,6‐Mes(2)C(6)H(3))(2)EF (E=P, As) generated the highly reactive phosphenium ion [(2,6‐Mes(2)C(6)H(3))(2)P](+) and the arsenium ion [(2,6‐Mes(2)C(6)H(3))(2)As](+), which immediately underwent intramolecular electrophilic substitution and formation of an 1,2,4‐trimethyl‐6‐mesityl‐5‐m‐terphenyl‐benzo[b]phospholium ion and an 1,2,4‐trimethyl‐6‐mesityl‐5‐m‐terphenyl‐benzo[b]arsolium ion, respectively. The formation of the latter involved a methyl group migration from the ortho‐position of a flanking mesityl group to the meta‐position. This reactivity of [(2,6‐Mes(2)C(6)H(3))(2)E](+) (E=P, As) is in sharp contrast to the related stibenium ion [(2,6‐Mes(2)C(6)H(3))(2)Sb](+) and bismuthenium ion [(2,6‐Mes(2)C(6)H(3))(2)Bi](+), which have been recently isolated and fully characterized (Angew. Chem. Int. Ed. 2018, 57, 10080–10084). On the basis of DFT calculations, a mechanism for the rearrangement of the phosphenium and arsenium ions into the phospholium and arsolium ions is proposed, which is not feasible for the stibenium and bismuthenium ions. John Wiley and Sons Inc. 2019-10-24 2019-11-22 /pmc/articles/PMC6900177/ /pubmed/31404472 http://dx.doi.org/10.1002/chem.201902520 Text en © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Communications Olaru, Marian Duvinage, Daniel Lork, Enno Mebs, Stefan Beckmann, Jens Transient Phosphenium and Arsenium Ions versus Stable Stibenium and Bismuthenium Ions |
title | Transient Phosphenium and Arsenium Ions versus Stable Stibenium and Bismuthenium Ions |
title_full | Transient Phosphenium and Arsenium Ions versus Stable Stibenium and Bismuthenium Ions |
title_fullStr | Transient Phosphenium and Arsenium Ions versus Stable Stibenium and Bismuthenium Ions |
title_full_unstemmed | Transient Phosphenium and Arsenium Ions versus Stable Stibenium and Bismuthenium Ions |
title_short | Transient Phosphenium and Arsenium Ions versus Stable Stibenium and Bismuthenium Ions |
title_sort | transient phosphenium and arsenium ions versus stable stibenium and bismuthenium ions |
topic | Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6900177/ https://www.ncbi.nlm.nih.gov/pubmed/31404472 http://dx.doi.org/10.1002/chem.201902520 |
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