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Lewis Superacidic Tellurenyl Cation‐Induced Electrophilic Activation of an Inert Carborane

The aryltellurenyl cation [2‐(tBuNCH)C(6)H(4)Te](+), a Lewis super acid, and the weakly coordinating carborane anion [CB(11)H(12)](−), an extremely weak Brønsted acid (pK (a)=131.0 in MeCN), form an isolable ion pair complex [2‐(tBuNCH)C(6)H(4)Te][CB(11)H(12)], in which the Brønsted acidity (pK (a)...

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Autores principales: Hejda, Martin, Duvinage, Daniel, Lork, Enno, Lyčka, Antonín, Černošek, Zdeněk, Macháček, Jan, Makarov, Sergey, Ketkov, Sergey, Mebs, Stefan, Dostál, Libor, Beckmann, Jens
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8596995/
https://www.ncbi.nlm.nih.gov/pubmed/34495561
http://dx.doi.org/10.1002/chem.202103181
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author Hejda, Martin
Duvinage, Daniel
Lork, Enno
Lyčka, Antonín
Černošek, Zdeněk
Macháček, Jan
Makarov, Sergey
Ketkov, Sergey
Mebs, Stefan
Dostál, Libor
Beckmann, Jens
author_facet Hejda, Martin
Duvinage, Daniel
Lork, Enno
Lyčka, Antonín
Černošek, Zdeněk
Macháček, Jan
Makarov, Sergey
Ketkov, Sergey
Mebs, Stefan
Dostál, Libor
Beckmann, Jens
author_sort Hejda, Martin
collection PubMed
description The aryltellurenyl cation [2‐(tBuNCH)C(6)H(4)Te](+), a Lewis super acid, and the weakly coordinating carborane anion [CB(11)H(12)](−), an extremely weak Brønsted acid (pK (a)=131.0 in MeCN), form an isolable ion pair complex [2‐(tBuNCH)C(6)H(4)Te][CB(11)H(12)], in which the Brønsted acidity (pK (a) 7.4 in MeCN) of the formally hydridic B−H bonds is dramatically increased by more than 120 orders of magnitude. The electrophilic activation of B−H bonds in the carborane moiety gives rise to a proton transfer from boron to nitrogen at slightly elevated temperatures, as rationalized by the isolation of a mixture of the zwitterionic isomers 12‐ and 7‐[2‐(tBuN{H}CH)C(6)H(4)Te(CB(11)H(11))] in ratios ranging from 62 : 38 to 80 : 20.
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spelling pubmed-85969952021-11-22 Lewis Superacidic Tellurenyl Cation‐Induced Electrophilic Activation of an Inert Carborane Hejda, Martin Duvinage, Daniel Lork, Enno Lyčka, Antonín Černošek, Zdeněk Macháček, Jan Makarov, Sergey Ketkov, Sergey Mebs, Stefan Dostál, Libor Beckmann, Jens Chemistry Communications The aryltellurenyl cation [2‐(tBuNCH)C(6)H(4)Te](+), a Lewis super acid, and the weakly coordinating carborane anion [CB(11)H(12)](−), an extremely weak Brønsted acid (pK (a)=131.0 in MeCN), form an isolable ion pair complex [2‐(tBuNCH)C(6)H(4)Te][CB(11)H(12)], in which the Brønsted acidity (pK (a) 7.4 in MeCN) of the formally hydridic B−H bonds is dramatically increased by more than 120 orders of magnitude. The electrophilic activation of B−H bonds in the carborane moiety gives rise to a proton transfer from boron to nitrogen at slightly elevated temperatures, as rationalized by the isolation of a mixture of the zwitterionic isomers 12‐ and 7‐[2‐(tBuN{H}CH)C(6)H(4)Te(CB(11)H(11))] in ratios ranging from 62 : 38 to 80 : 20. John Wiley and Sons Inc. 2021-09-28 2021-10-21 /pmc/articles/PMC8596995/ /pubmed/34495561 http://dx.doi.org/10.1002/chem.202103181 Text en © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://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
Hejda, Martin
Duvinage, Daniel
Lork, Enno
Lyčka, Antonín
Černošek, Zdeněk
Macháček, Jan
Makarov, Sergey
Ketkov, Sergey
Mebs, Stefan
Dostál, Libor
Beckmann, Jens
Lewis Superacidic Tellurenyl Cation‐Induced Electrophilic Activation of an Inert Carborane
title Lewis Superacidic Tellurenyl Cation‐Induced Electrophilic Activation of an Inert Carborane
title_full Lewis Superacidic Tellurenyl Cation‐Induced Electrophilic Activation of an Inert Carborane
title_fullStr Lewis Superacidic Tellurenyl Cation‐Induced Electrophilic Activation of an Inert Carborane
title_full_unstemmed Lewis Superacidic Tellurenyl Cation‐Induced Electrophilic Activation of an Inert Carborane
title_short Lewis Superacidic Tellurenyl Cation‐Induced Electrophilic Activation of an Inert Carborane
title_sort lewis superacidic tellurenyl cation‐induced electrophilic activation of an inert carborane
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8596995/
https://www.ncbi.nlm.nih.gov/pubmed/34495561
http://dx.doi.org/10.1002/chem.202103181
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