Type of Publication: | Journal article |
Publication status: | Published |
URI (citable link): | http://nbn-resolving.de/urn:nbn:de:bsz:352-2-v6a0gueiqvac7 |
Author: | Januszewski, Estera; Lorbach, Andreas; Grewal, Rekha; Bolte, Michael; Bats, Jan W.; Lerner, Hans-Wolfram; Wagner, Matthias |
Year of publication: | 2011 |
Published in: | Chemistry - A European Journal ; 17 (2011), 45. - pp. 12696-12705. - ISSN 0947-6539. - eISSN 1521-3765 |
Pubmed ID: | 22028273 |
DOI (citable link): | https://dx.doi.org/10.1002/chem.201101701 |
Summary: |
The targeted hydrolysis of the 9,10-dihydro-9,10-diboraanthracene adduct (Me2S)HB(C6H4)2BH(SMe2) (1) with 0.5 equiv of H2O leads to formation of the borinic acid anhydride [(Me2S)HB(C6H4)2B]2O (2) and thereby provides access to the field of unsymmetrically substituted 9,10-dihydro-9,10-diboraanthracenes. Compound 2 reacts with tBuC≡CH to give the corresponding vinyl derivative in an essentially quantitative conversion. Subsequent cleavage of the B-O-B bridge by LiAlH4 with formation of hydridoborate functionalities is possible but is accompanied by partial B-C(vinyl) bond degradation. This situation changes when the related mesityl derivative [MesB(C6H4)2B]2O (7) is employed, which can be synthesized from BrB(C6H4)2BBr (6) by treatment with 1 equiv of MesMgBr and subsequent hydrolysis. The reaction of 7 with LiAlH4 in tetrahydrofuran (THF) furnishes Li[MesB(C6H4)2BH2] (8); hydride elimination with Me3SiCl leads to formation of the THF adduct MesB(C6H4)2BH(THF) (9·THF). Alternatively, 7 can be transformed into the bromoborane MesB(C6H4)2BBr (10) by treatment with BBr3. A Br/H-exchange reaction between 10 and Et3SiH yields the donor-free borane MesB(C6H4)2BH (9), which forms B-H-B bridged dimers (9)2 in the solid state. The vinyl borane MesB(C6H4)2BC(H)=C(H)Mes (14) is accessible from MesC≡CH and either 9·THF or 9. Compared with the related compound Mes2BC(H)=C(H)Mes, the electronic absorption and emission spectra of 14 reveal bathochromic shifts of Δλ(abs)=17 nm and Δλ(em)=74 nm, which can be attributed to the rigid, fully delocalized π framework of the [MesB(C6H4)2B] chromophore.
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Subject (DDC): | 540 Chemistry |
Link to License: | In Copyright |
Bibliography of Konstanz: | Yes |
JANUSZEWSKI, Estera, Andreas LORBACH, Rekha GREWAL, Michael BOLTE, Jan W. BATS, Hans-Wolfram LERNER, Matthias WAGNER, 2011. Unsymmetrically Substituted 9,10-Dihydro-9,10-diboraanthracenes as Versatile Building Blocks for Boron-Doped π-Conjugated Systems. In: Chemistry - A European Journal. 17(45), pp. 12696-12705. ISSN 0947-6539. eISSN 1521-3765. Available under: doi: 10.1002/chem.201101701
@article{Januszewski2011-11-04Unsym-39249, title={Unsymmetrically Substituted 9,10-Dihydro-9,10-diboraanthracenes as Versatile Building Blocks for Boron-Doped π-Conjugated Systems}, year={2011}, doi={10.1002/chem.201101701}, number={45}, volume={17}, issn={0947-6539}, journal={Chemistry - A European Journal}, pages={12696--12705}, author={Januszewski, Estera and Lorbach, Andreas and Grewal, Rekha and Bolte, Michael and Bats, Jan W. and Lerner, Hans-Wolfram and Wagner, Matthias} }
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