Influence of the Steric Demand of the 2,4,6‐Trialkylphenyl Substituents on the Structures and Reactivity of Diarylzinc
Influence of the Steric Demand of the 2,4,6‐Trialkylphenyl Substituents on the Structures and Reactivity of Diarylzinc
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2,4,6-三烷基苯基取代基的空间需求对二芳基锌结构和反应活性的影响
DOI：
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发表时间：
2005
期刊：
影响因子：
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通讯作者：
K. Ruhlandt
中科院分区：
文献类型：
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作者：
M. Westerhausen;Manfred W. Ossberger;J. S. Alexander;K. Ruhlandt
2，4，6-三(叔丁基)苯基溴化镁与二氯化锌在四氢呋喃中发生格氏反应，生成单体双[2，4，6-三(叔丁基)苯基]锌(1)。由于叔丁基的空间需求，1具有弯曲的CZnC部分，并且船形的芳基呈交错构象。在1，2-二甲氧基乙烷(DME)和甲苯(1，2-二甲氧基乙烷-O，O‘)的混合溶剂中，1与铯发生金属转移反应，分离得到铯[2，4，6-三(叔丁基)苯酚](2)。在结晶状态下，通过酚氧原子的Cs-O键和另一个分子的芳基部分与铯离子的η6配位将这些分子连接起来，形成聚合物结构。此外，在固态中，铯离子通过与双齿乙醚分子键合和与相邻分子的叔丁基紧密接触来完成配位球。
The Grignard reaction of 2,4,6-tri(tert-butyl)phenylmagnesium bromide with zinc dichloride in THF yields monomeric bis[2,4,6-tri(tert-butyl)phenyl]zinc (1). Due to the steric demand of the tert-butyl groups 1 has a bent CZnC moiety and the boat-shaped aryl groups are in a staggered conformation. After the transmetallation of 1 with cesium in a solvent mixture of 1,2-dimethoxyethane (DME) and toluene (1,2-dimethoxyethane-O,O′)cesium [2,4,6-tri(tert-butyl)phenolate] (2) is isolated. A polymeric structure is formed in the crystalline state by linkage of these molecules via a Cs-O bond of the phenolate oxygen atoms and a η6-coordination of the aryl moiety of another molecule to the cesium cations. Furthermore, in the solid state the cesium cation completes his coordination sphere by bonds to a bidentate ether molecule and by close contacts to a tert-butyl group of a neighboring molecule.