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Pyridinamide Ion Pairs: Design Principles for Super-Nucleophiles in Apolar Organic Solvents
Burger, Veronika, Franta, Maximilian, O‘Donoghue, AnnMarie C., Ofial, Armin R., Gschwind, Ruth M.
und Zipse, Hendrik
(2025)
Pyridinamide Ion Pairs: Design Principles for Super-Nucleophiles in Apolar Organic Solvents.
The Journal of Organic Chemistry.
Veröffentlichungsdatum dieses Volltextes: 04 Feb 2025 05:26
Artikel
DOI zum Zitieren dieses Dokuments: 10.5283/epub.74812
Zusammenfassung
A comprehensive analytical protocol combining conductivity, diffusion-ordered NMR (DOSY), and photometric kinetic measurements is employed to analyze the nucleophilic reactivity of pyridinamide ion pairs in low-polarity organic solvents. The association patterns of these systems are found to strongly depend on cation size, with larger cations favoring the formation of cationic triple ion sandwich ...
A comprehensive analytical protocol combining conductivity, diffusion-ordered NMR (DOSY), and photometric kinetic measurements is employed to analyze the nucleophilic reactivity of pyridinamide ion pairs in low-polarity organic solvents. The association patterns of these systems are found to strongly depend on cation size, with larger cations favoring the formation of cationic triple ion sandwich complexes together with free and highly nucleophilic anions. Kinetic studies using the ionic strength-controlled benzhydrylium method demonstrate that pyridinamide ions exhibit significantly higher nucleophilicities as compared to established organocatalysts, particularly in low-polarity solvents. Nucleophilicities are furthermore found to correlate well with Brønsted basicities measured in water and with Lewis basicities calculated in dichloromethane. Taken together, these findings provide quantitative guidelines for the future design of highly active Lewis base catalysts.
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| Dokumentenart | Artikel | ||||
| Titel eines Journals oder einer Zeitschrift | The Journal of Organic Chemistry | ||||
| Verlag: | American Chemical Society (ACS) | ||||
|---|---|---|---|---|---|
| Datum | 30 Januar 2025 | ||||
| Institutionen | Chemie und Pharmazie > Institut für Organische Chemie > Arbeitskreis Prof. Dr. Ruth Gschwind | ||||
| Projekte |
Gefördert von:
Deutsche Forschungsgemeinschaft (DFG)
(426795949)
| ||||
| Identifikationsnummer |
| ||||
| Dewey-Dezimal-Klassifikation | 500 Naturwissenschaften und Mathematik > 540 Chemie | ||||
| Status | Veröffentlicht | ||||
| Begutachtet | Ja, diese Version wurde begutachtet | ||||
| An der Universität Regensburg entstanden | Zum Teil | ||||
| URN der UB Regensburg | urn:nbn:de:bvb:355-epub-748126 | ||||
| Dokumenten-ID | 74812 |
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