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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.show moreshow less

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Metadaten
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
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
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.
EU-Project number / Contract (GA) number:669054
OpenAIRE:OpenAIRE
Licence (German):License LogoDeutsches Urheberrecht