Direkt zum Inhalt

Burger, Veronika ; Franta, Maximilian ; O‘Donoghue, AnnMarie C. ; Ofial, Armin R. ; Gschwind, Ruth M. ; Zipse, Hendrik

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.



Beteiligte Einrichtungen


Details

DokumentenartArtikel
Titel eines Journals oder einer ZeitschriftThe Journal of Organic Chemistry
Verlag:American Chemical Society (ACS)
Datum30 Januar 2025
InstitutionenChemie und Pharmazie > Institut für Organische Chemie > Arbeitskreis Prof. Dr. Ruth Gschwind
Projekte
Gefördert von: Deutsche Forschungsgemeinschaft (DFG) (426795949)
Identifikationsnummer
WertTyp
10.1021/acs.joc.4c02668DOI
Dewey-Dezimal-Klassifikation500 Naturwissenschaften und Mathematik > 540 Chemie
StatusVeröffentlicht
BegutachtetJa, diese Version wurde begutachtet
An der Universität Regensburg entstandenZum Teil
URN der UB Regensburgurn:nbn:de:bvb:355-epub-748126
Dokumenten-ID74812

Bibliographische Daten exportieren

Nur für Besitzer und Autoren: Kontrollseite des Eintrags

nach oben