Anion complexation and migration in (8-silyl-1-naphthyl)boranes. Participation of hypervalent silicon.
Anion complexation and migration in (8-silyl-1-naphthyl)boranes. Participation of hypervalent silicon.
复制标题
(8-甲硅烷基-1-萘基)硼烷中的阴离子络合和迁移。
DOI：
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发表时间：
1986
影响因子：
15
通讯作者：
H. Katz
中科院分区：
文献类型：
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作者：
H. Katz
合成了通式为8-RMe/sub 2/Si-1-Me/sub 2/B-萘的化合物1-3，并研究了它们与F/sup -/的配合物。通过多核NMR和X射线晶体学确定了1 x F/sup -/（R = Me）的结构，揭示了F/sup -/与五配位Si之间的相互作用。由二甲基（8-碘-1-萘基）硅烷合成2（R = OEt）和由2合成3（R = F）通过分子内阴离子迁移和高价Si中间体进行。化合物2是唯一报道的与硼烷配位的甲硅烷基醚的实例。由于FMe/sub 2/Si在F/sup -/键合中的参与比Me/sub 3/Si增加，因此3 x F/sup-/比1 x F/sup -/更稳定。这项工作代表了第一次考虑硅作为一个参与者在双齿阴离子络合和第一次探索的双齿刘易斯酸，其中两个活性官能团是不同的。
Compounds 1-3, of general structure 8-RMe/sub 2/Si-1-Me/sub 2/B-naphthalene, were prepared, and their complexes with F/sup -/ were examined. The structure of 1 x F/sup -/ (R = Me) was determined by multinuclear NMR and X-ray crystallography, revealing an interaction between F/sup -/ and pentacoordinate Si. Syntheses of 2 (R = OEt) from dimethyl(8-iodo-1-naphthyl)silane and of 3 (R = F) from 2 proceeded via intramolecular anion migrations and hypervalent Si intermediates. Compound 2 is the only reported example of a silyl ether coordinated to a borane. The complex 3 x F/sup -/ was more stable than 1 x F/sup -/ because of increased participation of FMe/sub 2/Si in F/sup -/ bonding compared to Me/sub 3/Si. This work represents the first consideration of Si as a participant in bidentate anion complexation and the first exploration of bidentate Lewis acids in which the two active functional groups are different.