TY  - JOUR
A1  - Hausen, Hans-Dieter
A1  - Bessenbacher, Christian
A1  - Kaim, Wolfgang
T1  - Elektronenreiche Olefine, 2 Struktur und Elektrontransfer-Reaktivität des cyclisch σ/π-hyperkonjugierten Carbosilans 3,3,6,6-Tetrakis(trimethylsilyl)-1,4-cyclohexadien
T1  - 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
T2  - Zeitschrift für Naturforschung, B
N2  - 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.
KW  - Organosilicon Compounds
KW  - Molecular Conformation
KW  - Electron Transfer
KW  - Hyperconjugation
KW  - Electronic Structure
Y1  - 2014
UR  - http://publikationen.ub.uni-frankfurt.de/frontdoor/index/index/docId/72277
UR  - https://nbn-resolving.org/urn:nbn:de:hebis:30:3-722776
SN  - 1865-7117
SN  - 0932-0776
VL  - 43.1988
IS  - 9
SP  - 1087
EP  - 1093
PB  - Verlag der Zeitschrift für Naturforschung
CY  - Tübingen
ER  -