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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-)

Title data

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. Vol. 17 (7 March 2011) Issue 11 . - pp. 3238-3251.
ISSN 1521-3765
DOI: https://doi.org/10.1002/chem.201002277

Abstract in another language

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).

Further data

Item Type: Article in a journal
Refereed: Yes
Keywords: carboranes; cluster compounds; deboronation; NMR spectroscopy; selenium
Institutions of the University: Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Anorganic Chemistry I
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Anorganic Chemistry II > Chair Anorganic Chemistry II - Univ.-Prof. Dr. Rhett Kempe
Faculties
Faculties > Faculty of Biology, Chemistry and Earth Sciences
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Anorganic Chemistry II
Result of work at the UBT: Yes
DDC Subjects: 500 Science > 540 Chemistry
Date Deposited: 22 Mar 2018 14:31
Last Modified: 22 Mar 2018 14:31
URI: https://eref.uni-bayreuth.de/id/eprint/9881