Résumé
The isolation, characterization, and the first X-ray structures of a fluorenylium ion and its Lewis adducts with nitrogen- and phosphorus-centered Lewis bases are reported. Kinetics of the reactions of a series of fluorenylium ions with reference π-, σ-, and n-nucleophiles of various sizes and nucleophilicities allowed the interplay between electronic and structural parameters on the electrophilicities of these planarized tertiary carbenium ions to be elucidated. Structure–reactivity correlations and extensive comparisons of their reactivities with those of di- and triarylcarbenium ions are described. Quantitative determination of the electrofugalities of fluorenylium ions revealed to which extent they are complementing tritylium ions as protecting groups and how their tuning is possible. Determination of the equilibrium constants of the Lewis adducts formation between pyridines of calibrated Lewis basicities and phenylfluorenylium and tritylium ions allowed the determination of their Lewis acidities and to showcase the potential of these carbon-centered Lewis acids in catalysis.
langue originale | Anglais |
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Pages (de - à) | 623-630 |
Nombre de pages | 8 |
journal | Chemistry: A European Journal |
Volume | 23 |
Numéro de publication | 3 |
Les DOIs | |
Etat de la publication | Publié - 12 janv. 2017 |
Modification externe | Oui |
Empreinte digitale
Examiner les sujets de recherche de « Structures, Lewis Acidities, Electrophilicities, and Protecting Group Abilities of Phenylfluorenylium and Tritylium Ions ». Ensemble, ils forment une empreinte digitale unique.Ensembles de données
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CCDC 1495226: Experimental Crystal Structure Determination
Berionni, G. (Contributeur), Follet, E. (Contributeur) & Mayer, P. (Contributeur), Cambridge Crystallographic Data Centre, 1 janv. 2017
DOI: 10.5517/ccdc.csd.cc1m5x3t, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1m5x3t&sid=DataCite
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CCDC 1495228: Experimental Crystal Structure Determination
Berionni, G. (Contributeur), Follet, E. (Contributeur) & Mayer, P. (Contributeur), Cambridge Crystallographic Data Centre, 1 janv. 2017
DOI: 10.5517/ccdc.csd.cc1m5x5w, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1m5x5w&sid=DataCite
Ensemble de données
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CCDC 1495227: Experimental Crystal Structure Determination
Berionni, G. (Contributeur), Follet, E. (Contributeur) & Mayer, P. (Contributeur), Cambridge Crystallographic Data Centre, 1 janv. 2017
DOI: 10.5517/ccdc.csd.cc1m5x4v, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1m5x4v&sid=DataCite
Ensemble de données