(η(5):η(1)-C5Me4SiMe2CH2)(η(5)-(trimethylsilyl)tetramethylcyclopentadienyl)Ti | 195259-25-7

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: (η(5):η(1)-C5Me4SiMe2CH2)(η(5)-(trimethylsilyl)tetramethylcyclopentadienyl)Ti
• 英文别名: [Ti(η5-tetramethyl(trimethylsilyl)cyclopentadienyl)(η5:η1-C5Me4(SiMe2CH2))]；methanidyl-dimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane;titanium(3+);trimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane
• CAS: 195259-25-7
• 化学式: C₂₄H₄₁Si₂Ti
• 分子量: 433.641
• InChiKey: AERWWLXHCPFMJH-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：

  (η(5):η(1)-C5Me4SiMe2CH2)(η(5)-(trimethylsilyl)tetramethylcyclopentadienyl)Ti 、 氢气 以 氘代甲苯 为溶剂， 以87%的产率得到
  参考文献：
  名称：

  相应的钛茂-（η2-乙烯）或（η2-炔烃）配合物氢化中的十甲基钛茂氢化物中间体和较大的辅助配体作用

  摘要：

  钛茂[Cp * 2Ti]（Cp * =η5-C5Me5）及其衍生物[Cp *（η5：η1-C5Me4CH2）TiMe]和[Cp * 2Ti（η2-CH2= CH2）]反应的1H NMR研究在室温和低于1 bar的压力下使用二氢，发现形成了二氢化物[Cp * 2TiH2]（1），并同时释放了甲烷或乙烷，具体取决于有机金属反应物。随后产生的缓慢生成1 [Cp * 2TiH]（2）（2）的缓慢衰变是由原位形成的并经氢气压力控制的钛茂介导的。通过在氢气存在下蒸发新鲜[Cp * 2Ti]的己烷溶液而获得的晶体产物，其晶体要么在晶胞的不对称部分具有两个独立的分子1，要么在晶体中由1和[Cp * 2Ti]组成的共晶体。 2：1的比例。在室温下进行炔烃配合物[Cp * 2Ti（η2-R1C≡CR2）]的氢化（R1 = R2 = Me或Et），得到烷烃R1CH2CH2R2，除去氢后，定量地形成2。对于包含较大取代基的炔烃配合物，R1

  DOI：

  10.1039/c7dt01545c
• 作为产物：
  描述：

  (η⁵-C₅Me₄SiMe₃)₂TiCH₃ 以 甲苯 为溶剂， 以85%的产率得到(η(5):η(1)-C5Me4SiMe2CH2)(η(5)-(trimethylsilyl)tetramethylcyclopentadienyl)Ti
  参考文献：
  名称：

  Effect of the Trimethylsilyl Substituent on the Reactivity of Permethyltitanocene

  摘要：

  The presence of a trimethylsilyl substituent in place of one of the methyl groups of each of the cyclopentadienyl ligands of decamethyltitanocene enhances the thermal stability of the resulting complex, [Ti-II{eta(5)-C5Me4(SiMe3)}(2)] (1), and controls the products formed in thermolysis of its methyl derivatives. Titanocene 1 was found to be stable in toluene solution up to 90 degrees C, while under vacuum at 140 degrees C it liberated hydrogen to give the asymmetrical doubly tucked-in titanocene [Ti-II{eta(3):eta(4)-C5Me2(SiMe3)(CH2)(2)}{eta(5)-C5Me4(SiMe3)}] (3). The mono- and dimethyl derivatives of 1, the complexes [(TiMe)-Me-III{eta(5)-C5Me4(SiMe3)}(2)] (5) and [(TiMe2)-Me-IV{eta(5)-C5Me4(SiMe3)}(2)] (6), undergo thermolysis at lower temperature than do the corresponding permethyltitanocene derivatives and eliminate hydrogen from their trimethylsilyl group. Thus, the known [Ti-III{eta(5):eta(1)-C5Me4(SiMe2CH2)}{eta(5)-C5Me4(SiMe3)}] (4) was obtained from 5, and compound 6 afforded [Ti-II{eta(6):eta(1)-C5Me3(CH2)(SiMe2CH2)}{eta(5)-C5Me4(SiMe3)}] (7) at only 90 degrees C, both with liberation of methane. Crystal structures of 3, 5, and 7 were determined. DFT calculations for titanocene 1 revealed that the metal-cyclopentadienyl bonding is accomplished via a three-center-four-electron orbital interaction. An auxiliary long-range Si-C bond interaction with the Ti center was also established, providing a reason for the enhanced thermal stability of 1. The molecular orbitals participating in the exo methylene-titanium bonds for 3 and 7 are also three-centered and are compatible with the assignment of their activated ligands to eta(3):eta(4)-allyldiene and eta(6)-fulvene structures, respectively. Qualitatively, the much higher thermal stability of 3 and 7 compared to that of 1 is due to the exploitation of four d orbitals in the bonding molecular orbitals for 3 and 7 versus only two d orbitals for 1.

  DOI：

  10.1021/om070159l

文献信息

• Activation of the (Trimethylsilyl)tetramethylcyclopentadienyl Ligand in the [C₅Me₄(SiMe₃)]₂TiCl₂/Mg System, Yielding Intramolecular Si−CH₂−Mg and Si−CH₂−Ti Bonds. Molecular Structures of {[η⁵-C₅Me₄SiMe₂(μ-CH₂{<i>Mg</i>,<i>Mg</i>})][η⁵-C₅Me₄(SiMe₃)]Ti^III(μ-H)₂Mg(THF)}₂ and [η⁵:η¹-C₅Me₄SiMe₂CH₂][η⁵-C₅Me₄(SiMe₃)]Ti^III
  作者：Michal Horáček、Jörg Hiller、Ulf Thewalt、Miroslav Polášek、Karel Mach

  DOI：10.1021/om9701783

  日期：1997.9.1

  The reduction of [C5Me4(SiMe3)](2)TiCl2 by excess Mg in THF yields the paramagnetic compound [eta(5)-C5Me4SiMe2(mu-CH2Mg,Mg})][eta(5)-C5Me4(SiMe3)]Ti-III(mu-H)(2)Mg(THF)}(2) (3). In the presence of Me3SiC=CSiMe3 the same system affords the paramagnetic compound [eta(5):eta(1)-C5Me4SiMe2CH2][eta(5)-C5Me4(SiMe3)]Ti-III (4) in 75% yield. The crystal structures of 3 and 4 reveal that one SiMe3 group in each of the compounds has been activated by hydrogen abstraction. In centrosymmetric dimer 3, two titanocene-magnesium hydride-bridged units are held together by two methylene groups which link the two Mg atoms via a two-electron-three-center Mg-C-Mg bond. In the mononuclear 4, a regular Ti-CH2 sigma-bond (2.204(5) Angstrom) binds the central Ti atom to the eta(5):eta(1)-C5Me4SiMe2CH2 ligand.