Desymmetrization of dicationic diboranes by isomerization catalyzed by a nucleophile

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...

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Main Authors: Schön, Florian (Author) , Greb, Lutz (Author) , Kaifer, Elisabeth (Author) , Himmel, Hans-Jörg (Author)
Format: Article (Journal)
Language:English
Published: 17 March 2020
In: Angewandte Chemie. International edition
Year: 2020, Volume: 59, Issue: 23, Pages: 9127-9133
ISSN:1521-3773
DOI:10.1002/anie.202001640
Online Access:Verlag, kostenfrei, Volltext: https://doi.org/10.1002/anie.202001640
Verlag, kostenfrei, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202001640
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Author Notes:Florian Schön, Lutz Greb, Elisabeth Kaifer, and Hans-Jörg Himmel
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Summary: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.
Item Description:Gesehen am 15.07.2020
Physical Description:Online Resource
ISSN:1521-3773
DOI:10.1002/anie.202001640