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Wrackmeyer, Bernd ; Klimkina, Elena V. ; Milius, Wolfgang ; Bauer, Tobias ; Kempe, Rhett:
Synthesis and Reactivity of 4,5-[1,2-Dicarba-closo-dodecaborano(12)]-1,3-diselenacyclopentane : Opening of the Icosahedron to Give a Zwitterionic Intermediate and Conversion into 7,8-Dicarba-nido-undecaborate(1-).
In: Chemistry : a European Journal.
Bd. 17
(2011)
Heft 11
.
- S. 3238-3251.
ISSN 1521-3765
DOI: https://doi.org/10.1002/chem.201002277
Abstract
The reaction of the 1,2-diselenolato-1,2-dicarba-closo-dodecaborane(12) dianion [1,2-(1,2-C2B10H10)Se2]2− with dichloromethane (CH2Cl2 or CD2Cl2) in the presence of donor solvents gave 4,5-[1,2-dicarba-closo-dodecaborano(12)]-1,3-diselenacyclopentane, the title compound, which was characterized by X-ray structural analysis and NMR spectroscopy (1H, 11B, 13C, and 77Se). In the presence of pyridine, opening of the icosahedron took place, and a zwitterionic intermediate was isolated and fully characterized in the solid state by X-ray diffraction and in solution by multinuclear magnetic resonance techniques. Although such types of intermediates, prior to deboronation of the ortho-carborane cage, have been proposed several times, this is first example for which the structure has been confirmed unambiguously. This intermediate possesses a nido structure and contains a 7,8-dicarba-nido-undecaborate(1−) anion and a boronium cation, the latter with two pyridine rings linked to the boron atom, which has been extruded from the cage. It was shown that this process is reversible as long as the deboronation is not complete. The formation of the intermediate is accompanied by deboronation, which leads to the 7,8-dicarba-nido-undecaborate(1−) anion. The latter was prepared independently by conventional routes from the title compound, isolated as crystalline material as the tetrabutyl ammonium salt, and characterized by X-ray structural analysis and multinuclear magnetic resonance spectroscopy (1H, 11B, 13C, and 77Se).
Weitere Angaben
| Publikationsform: | Artikel in einer Zeitschrift |
|---|---|
| Begutachteter Beitrag: | Ja |
| Keywords: | carboranes; cluster compounds; deboronation; NMR spectroscopy; selenium |
| Institutionen der Universität: | Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie > Lehrstuhl Anorganische Chemie I Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie > Lehrstuhl Anorganische Chemie II > Lehrstuhl Anorganische Chemie II - Univ.-Prof. Dr. Rhett Kempe Fakultäten Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Chemie > Lehrstuhl Anorganische Chemie II |
| Titel an der UBT entstanden: | Ja |
| Themengebiete aus DDC: | 500 Naturwissenschaften und Mathematik > 540 Chemie |
| Eingestellt am: | 22 Mär 2018 14:31 |
| Letzte Änderung: | 31 Jan 2022 13:00 |
| URI: | https://eref.uni-bayreuth.de/id/eprint/9881 |