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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Detalles Bibliográficos
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
Descripción
Sumario: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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