bis(4-tert-butyl-2-methylcyclopenta-2,4-dien-1-yl)-dimethylsilane;dimethylazanide;zirconium(4+) | 181492-61-5

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: bis(4-tert-butyl-2-methylcyclopenta-2,4-dien-1-yl)-dimethylsilane;dimethylazanide;zirconium(4+)
• CAS: 181492-61-5；174081-11-9
• 化学式: C₂₆H₄₆N₂SiZr
• 分子量: 505.974
• InChiKey: QRISGQUAOBJPKO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  四(二甲氨基)锆 、 dimethylbis(2-methyl-4-tert-butylcyclopentadienyl)silane 以 甲苯 为溶剂， 以52%的产率得到bis(4-tert-butyl-2-methylcyclopenta-2,4-dien-1-yl)-dimethylsilane;dimethylazanide;zirconium(4+)
  参考文献：
  名称：

  Synthesis of Me₂Si-Bridged ansa-Zirconocenes by Amine Elimination

  摘要：

  Me(2)Si-bridged ansa-zirconocenes of interest for a-olefin polymerization catalysis are prepared in good yield by amine elimination reactions. The reaction of Me(2)Si(1-C5H4-3-(t)Bu)(2) (3) and Zr(NMe(2))(4) affords Me(2)Si(1-C5H3-3-(t)Bu)(2)Zr(NMe(2))(2) (4) in 95% NMR yield (rac/meso = 1/2) and pure meso-4 in 38% isolated yield. The reaction of Me(2)Si(1-C5H3-2-Me-4-(t)Bu)(2) (6) with Zr(NMe(2))(4) affords Me(2)Si(1-C5H2-2-Me-4-(t)Bu)(2)Zr(NMe(2))(2) (7) in 90% NMR yield (rac/meso = 2.5/1) and pure rac-7 in 52% isolated yield. The 1/2 rac-4/meso-4 and 2.5/1 rac-7/meso-7 ratios are the thermodynamic ratios, and the rac/meso isomerizations are catalyzed by NMe(2)H via reversible Zr-Cp bond aminolysis. The thermodynamic bias for meso-4 is ascribed to the ease of distortion of the metallocene framework of this diastereomer by a lateral deformation which reduces steric crowding between the amide ligands and the Cp substituents. The reaction of 6 and Zr(NEt(2))(4) proceeds only in 1,2-dichlorobenzene at 180 degrees C, affording Me(2)Si(1-C5H2-2-Me-4-(t)Bu)(2)ZrCl2 (rac-1) in 35% NMR yield (rac/meso = 3/1). The reaction of 6 and the piperidide complex Zr(NC5H10)(4) (m-xylene, 140 degrees C, 24 h) affords rac-Me(2)Si(1-C5H2-2-Me-4-(t)Bu)(2)Zr(NC5H10)(2) (rac-9) in 35% NMR yield (no meso detected) and pure rac-9 in 7% isolated yield. The reaction of 6 and the pyrrolidide complex Zr(NC4H8)(4) (m-xylene, 90 degrees C, 4h) affords Me(2)Si(1-C5H2-2-Me-4-(t)Bu)(2)Zr(NC4H8)(2) (10) in 80% NMR yield (rac/meso = 3/1) and pure rac-10 in 39% isolated yield. The molecular structure of rac-10 was determined by X-ray crystallography and exhibits severe crowding between the amide ligands and the Cp substituents. Treatment of rac-7 or rac-10 with Me(3)SiCl results in clean conversion to rac-1 without isomerization.

  DOI：

  10.1021/om9601054