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Bis(perfluoropinacolato)silane: A Neutral Silane Lewis Superacid Activates Si−F Bonds

Despite the earth abundance and easy availability of silicon, only few examples of isolable neutral silicon centered Lewis superacids are precedent in the literature. To approach the general drawbacks of limited solubility and unselective deactivation pathways, we introduce a Lewis superacid, based...

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Autores principales: Tschernuth, Florian S., Thorwart, Thaddäus, Greb, Lutz, Hanusch, Franziska, Inoue, Shigeyoshi
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/PMC9298387/
https://www.ncbi.nlm.nih.gov/pubmed/34570964
http://dx.doi.org/10.1002/anie.202110980
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author Tschernuth, Florian S.
Thorwart, Thaddäus
Greb, Lutz
Hanusch, Franziska
Inoue, Shigeyoshi
author_facet Tschernuth, Florian S.
Thorwart, Thaddäus
Greb, Lutz
Hanusch, Franziska
Inoue, Shigeyoshi
author_sort Tschernuth, Florian S.
collection PubMed
description Despite the earth abundance and easy availability of silicon, only few examples of isolable neutral silicon centered Lewis superacids are precedent in the literature. To approach the general drawbacks of limited solubility and unselective deactivation pathways, we introduce a Lewis superacid, based on perfluorinated pinacol substituents. The compound is easily synthesized on a gram‐scale as the corresponding acetonitrile mono‐adduct 1⋅(MeCN) and was fully characterized, including single crystal X‐ray diffraction analysis (SC‐XRD) and state‐of‐the‐art computations. Lewis acidity investigations by the Gutmann‐Beckett method and fluoride abstraction experiments indicate a Lewis superacidic nature. The challenging Si−F bond activation of Et(3)SiF is realized and promising catalytic properties are demonstrated, consolidating the potential applicability of silicon centered Lewis acids in synthetic catalysis.
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spelling pubmed-92983872022-07-21 Bis(perfluoropinacolato)silane: A Neutral Silane Lewis Superacid Activates Si−F Bonds Tschernuth, Florian S. Thorwart, Thaddäus Greb, Lutz Hanusch, Franziska Inoue, Shigeyoshi Angew Chem Int Ed Engl Communications Despite the earth abundance and easy availability of silicon, only few examples of isolable neutral silicon centered Lewis superacids are precedent in the literature. To approach the general drawbacks of limited solubility and unselective deactivation pathways, we introduce a Lewis superacid, based on perfluorinated pinacol substituents. The compound is easily synthesized on a gram‐scale as the corresponding acetonitrile mono‐adduct 1⋅(MeCN) and was fully characterized, including single crystal X‐ray diffraction analysis (SC‐XRD) and state‐of‐the‐art computations. Lewis acidity investigations by the Gutmann‐Beckett method and fluoride abstraction experiments indicate a Lewis superacidic nature. The challenging Si−F bond activation of Et(3)SiF is realized and promising catalytic properties are demonstrated, consolidating the potential applicability of silicon centered Lewis acids in synthetic catalysis. John Wiley and Sons Inc. 2021-11-05 2021-12-01 /pmc/articles/PMC9298387/ /pubmed/34570964 http://dx.doi.org/10.1002/anie.202110980 Text en © 2021 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 Communications
Tschernuth, Florian S.
Thorwart, Thaddäus
Greb, Lutz
Hanusch, Franziska
Inoue, Shigeyoshi
Bis(perfluoropinacolato)silane: A Neutral Silane Lewis Superacid Activates Si−F Bonds
title Bis(perfluoropinacolato)silane: A Neutral Silane Lewis Superacid Activates Si−F Bonds
title_full Bis(perfluoropinacolato)silane: A Neutral Silane Lewis Superacid Activates Si−F Bonds
title_fullStr Bis(perfluoropinacolato)silane: A Neutral Silane Lewis Superacid Activates Si−F Bonds
title_full_unstemmed Bis(perfluoropinacolato)silane: A Neutral Silane Lewis Superacid Activates Si−F Bonds
title_short Bis(perfluoropinacolato)silane: A Neutral Silane Lewis Superacid Activates Si−F Bonds
title_sort bis(perfluoropinacolato)silane: a neutral silane lewis superacid activates si−f bonds
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9298387/
https://www.ncbi.nlm.nih.gov/pubmed/34570964
http://dx.doi.org/10.1002/anie.202110980
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