| Tetradehydroadamantane-1,3,5,7-di- and tetracations and their helium and hydride inclusion complexes: spherical aromaticity and evidence for a bonding interaction between carbon and helium. | |
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MedLine Citation:
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PMID: 18785696 Owner: NLM Status: PubMed-not-MEDLINE |
Abstract/OtherAbstract:
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The unusual stability of the experimentally known 1,3-dehydro-5,7-adamantyl dication was previously explained by four-center two-electron aromaticity with three-dimensional (tetrahedral) topology. Magnetic criteria (ACID and ring-current analysis) now demonstrate that there is also a very strong contribution from hyperconjugation with all six methylene bridges. The delocalized system of electrons thus includes all valence electrons, and the structure, therefore, should rather be described as a spherically aromatic 50-electron system. The corresponding Td-symmetric tetracation with 48 electrons is antiaromatic and not a minimum structure. With a He atom or a hydride ion at the center of the cage, the tetracation is predicted to form a kinetically stable complex. Magnetic criteria demonstrate that the antiaromaticity is greatly reduced, and a bond analysis hints at bonding interactions between He (and H-) and the carbon atoms of the adamantane cage. |
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Authors:
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Götz Bucher; Felix Köhler; Rainer Herges |
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Publication Detail:
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Type: Journal Article Date: 2008-09-11 |
Journal Detail:
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Title: The journal of physical chemistry. A Volume: 112 ISSN: 1520-5215 ISO Abbreviation: J Phys Chem A Publication Date: 2008 Oct |
Date Detail:
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Created Date: 2008-10-03 Completed Date: 2008-12-03 Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 9890903 Medline TA: J Phys Chem A Country: United States |
Other Details:
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Languages: eng Pagination: 9906-10 Citation Subset: - |
Affiliation:
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Lehrstuhl fur Organische Chemie II, Ruhr-Universitat Bochum, Universitatsstrasse 150, 44801 Bochum, Germany. goebu@chem.gla.ac.uk |
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