INDENYLSILANES AND FLUORENYLSILANES - SYNTHESIS AND THERMAL DIASTEREOMERIZATION

被引:48
作者
CHEN, YX [1 ]
RAUSCH, MD [1 ]
CHIEN, JCW [1 ]
机构
[1] UNIV MASSACHUSETTS,DEPT POLYMER SCI & ENGN,DEPT CHEM,MAT RES LABS,AMHERST,MA 01003
关键词
D O I
10.1021/om00035a053
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Indenyl- and fluorenylmagnesium bromides were found to be particularly effective for the synthesis of LxSiCl4-x (L = Ind, Flu) and for their dimethyl and dimethoxy derivatives. The substitution of Si on indene occurs exclusively at the 1-position. Two diastereomers, the (R,R/S,S)-racemic and (R,S)-meso structures, were obtained and separated for (Ind)2SiX2 (X = Cl, OCH3, CH3). Thermal diastereomerization of racemic to meso structures has been shown to occur by the dynamic NMR method, and thermodynamic parameters have been determined. A possible mechanism involving intramolecular 1,3-metallotropic shifts for the diastereomerization process is proposed.
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页码:4607 / 4612
页数:6
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