Elektronenreiche Olefine, 2 Struktur und Elektrontransfer-Reaktivität des cyclisch σ/π-hyperkonjugierten Carbosilans 3,3,6,6-Tetrakis(trimethylsilyl)-1,4-cyclohexadien
Electron rich olefins, 2 structure and electron transfer reactivity of the cyclically σ/π-hyperconjugated carbosilane 3,3,6,6-tetrakis(trimethylsilyl)-1,4-cyclohexadiene
- Crystal and molecular structure analysis of the title compound 1, a most electron rich carbosilane, exhibits a shallow boat conformation for the cyclohexadiene ring which is shielded by four bulky Me3Si groups. Multiple hyperconjugative interaction occurs between the two non-conjugated olefinic π systems and the four rather long (192 pm) carbon-silicon o bonds which form an angle of about 34° with the assumed π axis. The HOMO destabilization caused by this unique structural arrangement explains the energetically facile formation and subsequent reactivity of the cation radical 1+ which was found to undergo oxidative desilylation to the aromatic 1,4-bis(trimethylsilyl) benzene precursor in the single electron transfer reaction with TCNE.
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| Author: | Hans-Dieter Hausen, Christian Bessenbacher, Wolfgang KaimORCiDGND |
|---|---|
| URN: | urn:nbn:de:hebis:30:3-722776 |
| DOI: | https://doi.org/10.1515/znb-1988-0902 |
| ISSN: | 1865-7117 |
| ISSN: | 0932-0776 |
| Parent Title (German): | Zeitschrift für Naturforschung, B |
| Publisher: | Verlag der Zeitschrift für Naturforschung |
| Place of publication: | Tübingen |
| Document Type: | Article |
| Language: | German |
| Date of Publication (online): | 2014/06/02 |
| Year of first Publication: | 1988 |
| Publishing Institution: | Universitätsbibliothek Johann Christian Senckenberg |
| Release Date: | 2024/01/27 |
| Tag: | Electron Transfer; Electronic Structure; Hyperconjugation; Molecular Conformation; Organosilicon Compounds |
| Volume: | 43.1988 |
| Issue: | 9 |
| Page Number: | 7 |
| First Page: | 1087 |
| Last Page: | 1093 |
| Institutes: | Biochemie, Chemie und Pharmazie / Biochemie und Chemie |
| Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |
| Sammlungen: | Universitätspublikationen |
| Licence (German): |  Creative Commons - Namensnennung-Nicht kommerziell-Keine Bearbeitung 3.0 |
