(η2-bis(trimethylsilyl)ethyne)bis(η5-tetramethyl(trimethylsilyl)cyclopentadienyl)titanium(II) | 195259-28-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (η2-bis(trimethylsilyl)ethyne)bis(η5-tetramethyl(trimethylsilyl)cyclopentadienyl)titanium(II)
• 英文别名: ((trimethylsilyl)tetramethylcyclopentadienyl)2Ti(η(2)-C2(SiMe3)2)；[(η(5)-C5Me4(SiMe3))2Ti(η(2)-Me3SiCCSiMe3)]；titanium(2+);trimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane;trimethyl(2-trimethylsilylethynyl)silane
• CAS: 195259-28-0
• 化学式: C₃₂H₆₀Si₄Ti
• 分子量: 605.05
• InChiKey: HFQRMDRVJFDACF-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：

  (η2-bis(trimethylsilyl)ethyne)bis(η5-tetramethyl(trimethylsilyl)cyclopentadienyl)titanium(II) 以 甲苯 为溶剂， 以72%的产率得到[Ti(η5-tetramethyl(trimethylsilyl)cyclopentadienyl)(η3:η4-C5Me2(SiMe3)(CH2)2)]
  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
• 作为产物：
  描述：

  [TiCl2(η5-C5Me4SiMe3)2] 、 二(三甲基甲硅烷基)乙炔 在 Mg 作用下， 以 四氢呋喃 为溶剂， 生成 (η2-bis(trimethylsilyl)ethyne)bis(η5-tetramethyl(trimethylsilyl)cyclopentadienyl)titanium(II) 、 (η(5):η(1)-C5Me4SiMe2CH2)(η(5)-(trimethylsilyl)tetramethylcyclopentadienyl)Ti 、 ((η(5)-C5Me4SiMe2(μ-CH2(Mg,Mg)))(η(5)-(trimethylsilyl)tetramethylcyclopentadienyl)Ti(μ-H)2Mg(C4H8O))2
  参考文献：
  名称：

  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{Mg,Mg})][η⁵-C₅Me₄(SiMe₃)]Ti^III(μ-H)₂Mg(THF)}₂ and [η⁵:η¹-C₅Me₄SiMe₂CH₂][η⁵-C₅Me₄(SiMe₃)]Ti^III

  摘要：

  The reduction of [C5Me4(SiMe3)](2)TiCl2 by excess Mg in THF yields the paramagnetic compound {[eta(5)-C5Me4SiMe2(mu-CH2{Mg,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.

  DOI：

  10.1021/om9701783

文献信息

• Bis[η⁵-tetramethyl(trimethylsilyl)cyclopentadienyl]titanium(II) and Its π-Complexes with Bis(trimethylsilyl)acetylene and Ethylene
  作者：Michal Horáček、Volkmar Kupfer、Ulf Thewalt、Petr Štěpnička、Miroslav Polášek、Karel Mach

  DOI：10.1021/om990286k

  日期：1999.8.1

  Thermally induced elimination of bis(trimethylsilyl)acetylene from its titanocene complex [η5-C5Me4(SiMe3)}2Ti(η2-Me3SiC⋮CSiMe3)] (1) afforded the stable titanocene [η5-C5Me4(SiMe3)}2TiII] (2) in high yield under mild conditions. Compound 2 exhibits paramagnetic line broadening of 1H NMR signals, although it is silent in EPR spectra down to −196 °C. The solid-state structure determination revealed

  从它的二茂钛络合物的双热诱导消除（三甲基甲硅烷基）乙炔[η 5 -C 5我4（森达3）} 2的Ti（η 2 -Me 3的SiC⋮CSiMe 3）]（1），得到稳定的二茂钛[ η 5 -C 5我4（森达3）} 2的Ti II ]（2）在温和条件下高收率。化合物2的顺磁性线展宽为1H NMR信号，尽管在低至-196°C的EPR光谱中无声。固态结构确定揭示了由于晶体学上施加的对称性，环戊二烯基环在2中的完全平行排列。复杂2与乙烯顺利反应，得到黄色η 2 -亚乙基络合物[η 5 -C 5我4（森达3）} 2的Ti（η 2 -CH 2 CH 2）]（3）。的结构1和3，通过单晶X射线衍射测定中，显示包含η弯曲-茂钛基部分2分别配位的Me 3 SiC⋮CSiMe 3和CH 2 CH 2配位体。