American Chemical Society
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Synthesis and Structure of cis-1,4-Di(1-pyrenyl)decamethylcyclohexasilane

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journal contribution
posted on 2003-04-23, 00:00 authored by Veronica E. M. Kaats-Richters, Thomas J. Cleij, Leonardus W. Jenneskens, Martin Lutz, Anthony L. Spek, Cornelis A. van Walree
The synthesis and structure of cis-1,4-di(1-pyrenyl)decamethylcyclohexasilane (2), one of the first cis-1,4-substituted cyclohexasilanes, are reported. This isomer is unexpectedly formed as the major product in the reaction of a mixture of trans- and cis-1,4-dichlorodecamethylcyclohexasilane (4a and 4b, respectively) with 1-pyrenyllithium. Reaction of 4a,b with phenyllithium showed that preferential formation of the cis-product is a general feature of this kind of reaction. According to the X-ray crystal structures of two different solvates, the cyclohexasilane ring in 2 adopts a unique boatlike geometry, with the pyrenyl substituents occupying an equatorial or bisectional position. 1H NMR data indicate that a boatlike geometry also occurs in solution. Furthermore, the X-ray crystal structure of trans-1,4-dihydrodecamethylcyclohexasilane, which is an intermediate in the synthetic pathway to 2, is reported.