Desymmetrization of dicationic diboranes by isomerization catalyzed by a nucleophile

• Verfasst von: Schön, Florian [VerfasserIn]
• Verfasst von: Greb, Lutz [VerfasserIn]
• Verfasst von: Kaifer, Elisabeth [VerfasserIn]
• Verfasst von: Himmel, Hans-Jörg [VerfasserIn]
• Titel: Desymmetrization of dicationic diboranes by isomerization catalyzed by a nucleophile
• Verf.angabe: Florian Schön, Lutz Greb, Elisabeth Kaifer, and Hans-Jörg Himmel
• E-Jahr: 2020
• Jahr: 17 March 2020
• Umfang: 7 S.
• Fussnoten: Gesehen am 15.07.2020
• Titel Quelle: Enthalten in: Angewandte Chemie / International edition
• Ort Quelle: Weinheim : Wiley-VCH, 1962
• Jahr Quelle: 2020
• Band/Heft Quelle: 59(2020), 23, Seite 9127-9133
• ISSN Quelle: 1521-3773
• DOI: doi:10.1002/anie.202001640
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: diborane
• Sach-SW: dications
• Sach-SW: electrophilic compounds
• Sach-SW: guanidine
• Sach-SW: isomerization
• K10plus-PPN: 1724894994
• K10plus-PPN:
  Universitätsbibliothek
• Lokale URL UB: Zum Volltext

Abstract

Cationic monoboranes exhibit a rich chemistry. By constrast, only a few cationic diboranes are known, that all are symmetrically substituted. In this work, the first unsymmetrically substituted dicationic diboranes, featuring sp2-sp2-hybridized boron atoms, are reported. The compounds are formed by intramolecular rearrangement from preceding isomeric symmetrically substituted dicationic diboranes, a process that is catalyzed by nucleophiles. From the temperature-dependence of the isomerization rate, activation parameters for this unprecedented rearrangement are derived. The difference in fluoride ion affinity between the two boron atoms and the bonding situation in these unique unsymmetrical dicationic diboranes are evaluated.