A chemiluminescent tetraaryl diborane(4) tetraanion
- Two subvalent, redox-active diborane(4) anions, [3]4− and [3]2−, carrying exceptionally high negative charge densities are reported: Reduction of 9-methoxy-9-borafluorene with Li granules without stirring leads to the crystallization of the B(sp3)−B(sp2) diborane(5) anion salt Li[5]. [5]− contains a 2,2′-biphenyldiyl-bridged B−B core, a chelating 2,2′-biphenyldiyl moiety, and a MeO substituent. Reduction of Li[5] with Na metal gives the Na+ salt of the tetraanion [3]4− in which two doubly reduced 9-borafluorenyl fragments are linked via a B−B single bond. Comproportionation of Li[5] and Na4[3] quantitatively furnishes the diborane(4) dianion salt Na2[3], the doubly boron-doped congener of 9,9′-bis(fluorenylidene). Under acid catalysis, Na2[3] undergoes a formal Stone–Wales rearrangement to yield a dibenzo[g,p]chrysene derivative with B=B core. Na2[3] shows boron-centered nucleophilicity toward n-butyl chloride. Na4[3] produces bright blue chemiluminescence when exposed to air.
Author: | Hendrik Budy, Thomas Kaese, Michael BolteORCiD, Hans-Wolfram LernerORCiDGND, Matthias WagnerORCiD |
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URN: | urn:nbn:de:hebis:30:3-639271 |
DOI: | https://doi.org/10.1002/anie.202106980 |
ISSN: | 1521-3773 |
Parent Title (German): | Angewandte Chemie |
Publisher: | Wiley-VCH |
Place of publication: | Weinheim |
Document Type: | Article |
Language: | English |
Date of Publication (online): | 2021/06/23 |
Date of first Publication: | 2021/06/23 |
Publishing Institution: | Universitätsbibliothek Johann Christian Senckenberg |
Release Date: | 2022/04/05 |
Tag: | 9-borafluorene; boryl anions; chemiluminescence; redox chemistry; subvalent compounds |
Volume: | 60 |
Issue: | 35 |
Page Number: | 9 |
First Page: | 19397 |
Last Page: | 19405 |
Note: | Open access funding enabled and organized by Projekt DEAL. |
HeBIS-PPN: | 493370447 |
Institutes: | Biochemie, Chemie und Pharmazie |
Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |
Sammlungen: | Universitätspublikationen |
Licence (German): | Creative Commons - Namensnennung-Nicht kommerziell - Keine Bearbeitung 4.0 |