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Engineering a Small HOMO-LUMO Gap and Intramolecular B–B Hydroarylation by Diborene/Anthracene Orbital Intercalation
Please always quote using this URN: urn:nbn:de:bvb:20-opus-148126
- 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 π(C\(_{14}\)) systems perpendicular to the diborene π(B=B) system. This twisted conformation allows for intercalation of the relatively high-lying π(B=B) orbital and the low-lying π* orbital of the anthryl moiety with no significant conjugation, resulting in a small HOMO-LUMO gap (HLG) and ultimately an unprecedentedThe 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 π(C\(_{14}\)) systems perpendicular to the diborene π(B=B) system. This twisted conformation allows for intercalation of the relatively high-lying π(B=B) orbital and the low-lying π* orbital of the anthryl moiety with no significant conjugation, resulting in a small HOMO-LUMO gap (HLG) and ultimately an unprecedented anthryl B–B bond hydroarylation. 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, λ\(_{onset}\) = 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 C\(^1\)–H bonds of 8 were cleaved to give the cyclic 1,9-diboraanthracene 9.…
Author: | Sunewang R. Wang, Merle Arrowsmith, Julian Böhnke, Holger BraunschweigORCiD, Theresa Dellermann, Rian D. Dewhurst, Hauke Kelch, Ivo Krummenacher, James D. Mattock, Jonas H. Müssig, Torsten Thiess, Alfredo Vargas, Jiji Zhang |
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URN: | urn:nbn:de:bvb:20-opus-148126 |
Document Type: | Preprint |
Faculties: | Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie |
Language: | English |
Parent Title (English): | Angewandte Chemie, International Edition |
Year of Completion: | 2017 |
Volume: | 56 |
Issue: | 27 |
Pagenumber: | 8009–8013 |
Source: | Angewandte Chemie International Edition Engl. 2017 Jun 26; 56 (27): 8009-8013. doi:10.1002/anie.201704063 |
DOI: | https://doi.org/10.1002/anie.201704063 |
Sonstige beteiligte Institutionen: | The University of Sussex |
Sonstige beteiligte Institutionen: | The Chinese University of Hong Kong |
Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 546 Anorganische Chemie |
Tag: | boron; borylation; diborenes; hydroarylation; small HOMO-LUMO gap |
Release Date: | 2017/06/27 |
EU-Project number / Contract (GA) number: | 669054 |
OpenAIRE: | OpenAIRE |
Note: | This is the pre-peer reviewed version of the following article: S. R. Wang, M. Arrowsmith, J. Böhnke, H. Braunschweig, T. Dellermann, R. D. Dewhurst, H. Kelch, I. Krummenacher, J. D. Mattock, J. H. Müssig, T. Thiess, A. Vargas, J. Zhang, Angew. Chem. Int. Ed. 2017, 56, 8009., which has been published in final form at DOI: 10.1002/anie.201704063. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. |
Licence (German): | Deutsches Urheberrecht |