bis(3-tert-butylcyclopenta-2,4-dien-1-yl)-dimethylsilane;dimethylazanide;zirconium(4+) | 181492-60-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: bis(3-tert-butylcyclopenta-2,4-dien-1-yl)-dimethylsilane;dimethylazanide;zirconium(4+)
• CAS: 181492-60-4；181364-04-5
• 化学式: C₂₄H₄₂N₂SiZr
• 分子量: 477.92
• InChiKey: XKIAATJLPWVPDU-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

• 作为反应物：
  描述：

  三甲基铝 、 bis(3-tert-butylcyclopenta-2,4-dien-1-yl)-dimethylsilane;dimethylazanide;zirconium(4+) 以 甲苯 为溶剂， 以58.3%的产率得到[meso-Me2Si(C5H3-3-CMe3)2]ZrMe2
  参考文献：
  名称：

  已单的合成和双桥联袢-Zirconocene氢化物。一个不寻常的混合价三聚氢化物的形成的H反应2与{（ME 2 Si）的2（η 5 -C 5 H ^ 3）2 } Zr的（CH 3）2和生成一氧化二的通过N反应复合物2与二茂锆

  摘要：

  一系列的单和双桥接柄-zirconocene二氢化络合物已经从相应的二甲基配合物的氢化制备。对于单一的[SiMe 2 ]桥接的物质，在25°C时氢化反应很容易，而对于[SiMe 2 ]桥接的双络合物，则在87°C的几天内发生氢化。{的加氢内消旋-Me 2的Si（η 5 -C 5 H ^ 3 -3-CME 3）2 } ZrMe 2，得到同分异构的二聚dihydrides [{消旋-Me 2的Si（η 5 -C 5 H ^3 -3-CME 3）2 } ZRH] 2（μ 2 -H）2，其中之一已被其特征在于，X射线衍射。的外消旋的Me异构体2的Si（η 5 -C 5 H ^ 2 -2-森达3 -4-CME 3）2 ZrMe 2（BpZrMe 2）与二氢发生反应，得到的单体的第一示例柄-zirconocene二氢化，{外消旋-Me 2的Si（η 5 -C 5 H ^ 2 -2-森达3-4-CMe 3）2

  DOI：

  10.1021/om000739h
• 作为产物：
  描述：

  四(二甲氨基)锆 、 dimethylbis(3-tert-butylcyclopentadienyl)silane 以 甲苯 为溶剂， 以38%的产率得到bis(3-tert-butylcyclopenta-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