Anthryl Diborene-ACIE.pdf (794.05 kB)
Engineering a small HOMO-LUMO gap and intramolecular C-H borylation by diborene/anthracene orbital intercalation
journal contribution
posted on 2023-06-09, 06:21 authored by Sunewang R Wang, Merle Arrowsmith, Julian Böhnke, Holger Braunschweig, Theresa Dellermann, Rian Dewhurst, Hauke Kelch, Ivo Krummenacher, James D Mattock, Jonas Müssig, Thorsten Thiess, Alfredo VargasAlfredo Vargas, Jiji ZhangThe diborene 1 was synthesized by reduction of a mixture of 1,2-di-9-anthryl-1,2-dibromodiborane(4) (6) and trimethylphosphine with potassium graphite. The X-ray structure of 1 shows the two anthryl rings to be parallel and their p(C14) systems perpendicular to the diborene p(B=B) system. This twisted conformation allows for intercalation of the relatively high-lying p(B=B) orbital and the low-lying p* orbital of the anthryl moiety with no significant conjugation, resulting in a small HOMO-LUMO gap (HLG) and ultimately an anthryl C-H borylation. The HLG of 1 was estimated to be 1.57 eV from the onset of the long wavelength band in its UV-vis absorption spectrum (THF, ?onset = 788 nm). The oxidation of 1 with elemental selenium afforded diboraselenirane 8 in quantitative yield. By oxidative abstraction of one phosphine ligand by another equivalent of elemental selenium, the B-B and C1-H bonds of 8 were cleaved to give the cyclic 1,9-diborylanthracene 9.
History
Publication status
- Published
File Version
- Accepted version
Journal
Angewandte Chemie International EditionISSN
1433-7851Publisher
WileyExternal DOI
Issue
27Volume
56Page range
8009-8013Department affiliated with
- Chemistry Publications
Full text available
- Yes
Peer reviewed?
- Yes
Legacy Posted Date
2017-06-05First Open Access (FOA) Date
2018-06-06First Compliant Deposit (FCD) Date
2017-06-05Usage metrics
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