Bifunctional Fluorophosphonium Triflates as Intramolecular Frustrated Lewis Pairs: Reversible CO(2) Sequestration and Binding of Carbonyls, Nitriles and Acetylenes

Electrophilic fluorophosphonium triflates bearing pyridyl (3[OTf]) or imidazolyl (4[OTf])‐substituents act as intramolecular frustrated Lewis pairs (FLPs) and reversibly form 1 : 1 adducts with CO(2) (5 (+) and 6 (+)). An unusual and labile spirocyclic tetrahedral intermediate (7 (2+)) is observed i...

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Autores principales: Guo, Chun‐Xiang, Schwedtmann, Kai, Fidelius, Jannis, Hennersdorf, Felix, Dickschat, Arne, Bauzá, Antonio, Frontera, Antonio, Weigand, Jan J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8518062/
https://www.ncbi.nlm.nih.gov/pubmed/34432918
http://dx.doi.org/10.1002/chem.202102382
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author Guo, Chun‐Xiang
Schwedtmann, Kai
Fidelius, Jannis
Hennersdorf, Felix
Dickschat, Arne
Bauzá, Antonio
Frontera, Antonio
Weigand, Jan J.
author_facet Guo, Chun‐Xiang
Schwedtmann, Kai
Fidelius, Jannis
Hennersdorf, Felix
Dickschat, Arne
Bauzá, Antonio
Frontera, Antonio
Weigand, Jan J.
author_sort Guo, Chun‐Xiang
collection PubMed
description Electrophilic fluorophosphonium triflates bearing pyridyl (3[OTf]) or imidazolyl (4[OTf])‐substituents act as intramolecular frustrated Lewis pairs (FLPs) and reversibly form 1 : 1 adducts with CO(2) (5 (+) and 6 (+)). An unusual and labile spirocyclic tetrahedral intermediate (7 (2+)) is observed in CO(2)‐pressurized (0.5–2.0 bar) solutions of cation 4 (+) at low temperatures, as demonstrated by variable‐temperature NMR studies, which were confirmed crystallographically. In addition, cations 3 (+) and 4 (+) actively bind carbonyls, nitriles and acetylenes by 1,3‐dipolar cycloaddition, as shown by selected examples.
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spelling pubmed-85180622021-10-21 Bifunctional Fluorophosphonium Triflates as Intramolecular Frustrated Lewis Pairs: Reversible CO(2) Sequestration and Binding of Carbonyls, Nitriles and Acetylenes Guo, Chun‐Xiang Schwedtmann, Kai Fidelius, Jannis Hennersdorf, Felix Dickschat, Arne Bauzá, Antonio Frontera, Antonio Weigand, Jan J. Chemistry Communications Electrophilic fluorophosphonium triflates bearing pyridyl (3[OTf]) or imidazolyl (4[OTf])‐substituents act as intramolecular frustrated Lewis pairs (FLPs) and reversibly form 1 : 1 adducts with CO(2) (5 (+) and 6 (+)). An unusual and labile spirocyclic tetrahedral intermediate (7 (2+)) is observed in CO(2)‐pressurized (0.5–2.0 bar) solutions of cation 4 (+) at low temperatures, as demonstrated by variable‐temperature NMR studies, which were confirmed crystallographically. In addition, cations 3 (+) and 4 (+) actively bind carbonyls, nitriles and acetylenes by 1,3‐dipolar cycloaddition, as shown by selected examples. John Wiley and Sons Inc. 2021-08-25 2021-10-01 /pmc/articles/PMC8518062/ /pubmed/34432918 http://dx.doi.org/10.1002/chem.202102382 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
Guo, Chun‐Xiang
Schwedtmann, Kai
Fidelius, Jannis
Hennersdorf, Felix
Dickschat, Arne
Bauzá, Antonio
Frontera, Antonio
Weigand, Jan J.
Bifunctional Fluorophosphonium Triflates as Intramolecular Frustrated Lewis Pairs: Reversible CO(2) Sequestration and Binding of Carbonyls, Nitriles and Acetylenes
title Bifunctional Fluorophosphonium Triflates as Intramolecular Frustrated Lewis Pairs: Reversible CO(2) Sequestration and Binding of Carbonyls, Nitriles and Acetylenes
title_full Bifunctional Fluorophosphonium Triflates as Intramolecular Frustrated Lewis Pairs: Reversible CO(2) Sequestration and Binding of Carbonyls, Nitriles and Acetylenes
title_fullStr Bifunctional Fluorophosphonium Triflates as Intramolecular Frustrated Lewis Pairs: Reversible CO(2) Sequestration and Binding of Carbonyls, Nitriles and Acetylenes
title_full_unstemmed Bifunctional Fluorophosphonium Triflates as Intramolecular Frustrated Lewis Pairs: Reversible CO(2) Sequestration and Binding of Carbonyls, Nitriles and Acetylenes
title_short Bifunctional Fluorophosphonium Triflates as Intramolecular Frustrated Lewis Pairs: Reversible CO(2) Sequestration and Binding of Carbonyls, Nitriles and Acetylenes
title_sort bifunctional fluorophosphonium triflates as intramolecular frustrated lewis pairs: reversible co(2) sequestration and binding of carbonyls, nitriles and acetylenes
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8518062/
https://www.ncbi.nlm.nih.gov/pubmed/34432918
http://dx.doi.org/10.1002/chem.202102382
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