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Engineering a small HOMO-LUMO gap and intramolecular C-H borylation by diborene/anthracene orbital intercalation

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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 Zhang
The 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 Edition

ISSN

1433-7851

Publisher

Wiley

Issue

27

Volume

56

Page range

8009-8013

Department affiliated with

  • Chemistry Publications

Full text available

  • Yes

Peer reviewed?

  • Yes

Legacy Posted Date

2017-06-05

First Open Access (FOA) Date

2018-06-06

First Compliant Deposit (FCD) Date

2017-06-05

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