Cargando…

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...

Descripción completa

Detalles Bibliográficos
Autores principales: Olaru, Marian, Duvinage, Daniel, Lork, Enno, Mebs, Stefan, Beckmann, Jens
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2019
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
_version_ 1783477298288132096
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
work_keys_str_mv AT olarumarian transientphospheniumandarseniumionsversusstablestibeniumandbismutheniumions
AT duvinagedaniel transientphospheniumandarseniumionsversusstablestibeniumandbismutheniumions
AT lorkenno transientphospheniumandarseniumionsversusstablestibeniumandbismutheniumions
AT mebsstefan transientphospheniumandarseniumionsversusstablestibeniumandbismutheniumions
AT beckmannjens transientphospheniumandarseniumionsversusstablestibeniumandbismutheniumions