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The reaction of ( t BuO) 2 Si(Cl)Vi (3) with Li t Bu has been investigated in pentane or toluene (non-polar) and mixtures of pentane or toluene with THF (polar), respectively, in order to gain information about the influence of substituents and the polarity of the solvent on the reaction mechanism. In accord with earlier results, using Me 2 Si(Cl)Vi (1) [8] or t Bu 2 Si(Cl)Vi (2) [5] as precursors, the course of reaction in non-polar solvents is dominated by 1,2-elimination of LiCl from the α-lithio intermediate R 2 Si(Cl)CH(Li)CH 2 H t Bu yielding 1,1,3,3-tetra(tertbutoxy)-1,3-disilacyclobutane (4) via the corresponding silaethene derivative. On the other hand, the presence of small amounts (5% by volume) of THF in the solvent system leads to a considerable decrease in the yield of 4 and favours secondary reactions of the α-lithio derivative by solvate formation giving chain compounds like ( t BuO) 2 Si(X)CH 2 CH 2  t Bu (X = Cl,  t Bu) and ( t BuO) 2 Si(CH=CH t Bu)Si(O t Bu) 2 CH 2 CH 2  t Bu (5b). MNDO calculations on the model compounds Me 2 Si=CH 2 , Me 2 Si=CH 2  · OH 2  and (HO) 2 Si=CH 2 , (HO) 2 Si=CH 2  · OH 2 , respectively, show that for the gas phase molecules the formation of the dimethyl derivatives from the corresponding α-lithio intermediate is less endothermic than that of the dihydroxy analogues. Therefore, the differences observed in the product pattern of the reactions of 1 and 3, respectively, especially in polar systems, can only be explained by a combination of substituent and solvent effects on the kinetics.

zeitschrift für naturforschung b

Silaethene, XIV [1] Bildung und Reaktivität von 1,1-Di-tert-butoxy-2-neopentylsilaethen ( t BuO) 2 Si = CHNp / Silaethenes, XIV [1] Formation and Reactivity of 1,1-Di-tert-butoxy-2-neopentyl Silaethene ( t BuO) 2 Si=CHNp