[TiCl2(η5-C5Me4t-Bu)2] | 913614-47-8

• 英文名称: [TiCl2(η5-C5Me4t-Bu)2]
• 英文别名: [TiCl₂(η⁵-C₅Me₄t-Bu)₂]
• CAS: 913614-47-8
• 化学式: C₂₆H₄₂Cl₂Ti
• 分子量: 473.405
• InChiKey: BXWQIRRASFPRON-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [TiCl2(η5-C5Me4t-Bu)2] 在 Mg 作用下， 以 四氢呋喃 为溶剂， 生成 [TiCl(η5-C5Me4(t-Bu))2]
  参考文献：
  名称：

  Thermolysis of titanocene methyl compounds bearing t-butyl- and benzyltetramethylcyclopentadienyl ligands

  摘要：

  Elimination of methane during thermolysis of title compounds results in the formation of sigma-Ti-C bond to t-butyl or benzyl group. The t-butyl-containing titanocene methyl compound [Ti(III)Me(eta(5)-C(5)Me(4)t-Bu)(2)] (5) eliminates methane at 110 degrees C to give cleanly [Ti(III)(eta(5):eta(1)-C5Me4CMe2CH2)(eta(5)-C(5)Me(4)t-Bu)] (6). The methyl derivative of analogous benzyl-containing titanocene [Ti(III)Me(eta(5)-C5Me4CH2Ph)(2)] was not isolated because it eliminated methane at ambient temperature to give [Ti(III)(eta(5):eta(1)-C5Me4CH2-o-C6H4)(eta(5)-C5Me4CH2Ph)] (7) with one phenyl ring linked to titanium atom in ortho-position. The corresponding titanocene dimethyl compound [TiMe2{eta(5)-C(5)Me(4)t-Bu)}(2)] (9) eliminates two methane molecules at 110 degrees C to give the singly tucked-in 1,1-dimethylethane-1,2-diyl-tethered titanocene [Ti{eta(5):eta(1):eta(1)-C5Me3(CH2)(CMe2CH2)}(eta(5)-C(5)Me(4)t-Bu)] (11). In distinction, the analogous benzyl derivative [TiMe2(eta(5)-C5Me4CH2Ph)(2)] (10) eliminates at 110 degrees C only one methane molecule to afford [TiMe(eta(5):eta(1)-C5Me4CH2-o-C6H4)(eta(5)-C5Me4CH2Ph)] (12) containing one phenyl group attached to titanium in o-position and one methyl group persisting on the titanium atom. This compound is stable at 150 degrees C for at least 3 h. The crystal structures of 5, 6, 7, and 10 were determined. (c) 2009 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2009.01.039

文献信息

• Ethene Complexes of Bulky Titanocenes, Their Thermolysis, and Their Reactivity toward 2-Butyne
  作者：Jiří Pinkas、Ivana Císařová、Róbert Gyepes、Jiří Kubišta、Michal Horáček、Karel Mach

  DOI：10.1021/om300461k

  日期：2012.8.13

  single-crystal structure with linear geometry for 10. The ethene complexes 1–4 differed in their reactivity toward but-2-yne: compounds 1 and 4 yielded the respective [Ti(IV)(η1: η1-CH2CH2CMe═CMe)(Cp′)2] 2,3-dimethyltitanacyclopent-2-ene complexes 15 and 16, whereas 2 and 3 replaced ethene with but-2-yne, affording the [Ti(II)(η2-MeC≡CMe)(Cp′)2] complexes 17 and 18, respectively. Crystal structures of 2, 4

  二茂钛的乙烯复合物钛[Ti（II）（η 2 -C 2 H ^ 4）（CP'）2 ]为CP'=η 5 -C 5我5（1），η 5 -C 5我4吨-Bu（2），η 5 -C 5我4森达3（3），和η 5 -C 5 HME 4（4）通过还原对应的二茂钛二氯化物与乙烯的存在下在镁THF中制备。热解1–在最高100°C的甲苯溶液中– 3消除了乙烷，分别提供了干净地双重填充的钛茂化合物5 – 7。在NMR管中使用2和3进行的实验证明，首先形成了对称异构体6a和7a，并将它们热异构化为热力学更稳定的不对称异构体6b和7b。通过DFT方法计算的7a和7b之间的能量差为15.3kJ / mol。热解4 in m-二甲苯需要135°C的温度，才能提供8b > 8a和“二聚脱氢-茂钛” 9的混合物，作为氢提取的同时产物。与此相反，以热解在溶剂中，对其进行加热1和2在高真空中于135℃导致已知二茂钛的升华钛[Ti（C