[(η5-C5Me4CMe3)2Ti] | 808132-88-9

• 英文名称: [(η5-C5Me4CMe3)2Ti]
• CAS: 808132-88-9
• 化学式: C₂₆H₄₂Ti
• 分子量: 402.499
• InChiKey: CPVQBJSFALDNME-UHFFFAOYSA-N

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：

  [(η5-C5Me4CMe3)2Ti] 、 氮 以 正戊烷 为溶剂， 生成 [(η5-C5Me4CMe3)2Ti(N2)2]
  参考文献：
  名称：

  Dinitrogen Activation by Titanium Sandwich Complexes

  摘要：

  The activation of dinitrogen by titanium sandwich complexes of the general form (eta5-C5Me4R)2Ti (R = CHMe2, CMe3, SiMe3) has been systematically investigated. Low-temperature, in situ, solution infrared spectroscopy has allowed detection of monomeric bis-dinitrogen complexes of titanium that are isostructural with more familiar dicarbonyl derivatives. One example, (eta5-C5Me4CHMe2)2Ti(N2)2, has also been characterized by X-ray diffraction and reveals weakly activated dinitrogen ligands. From the solution IR data, the relative azophilicity of the titanium sandwich complexes has been established and increases with smaller cyclopentadienyl substituents.

  DOI：

  10.1021/ja045884r
• 作为产物：
  描述：

  [TiCl(η5-C5Me4(t-Bu))2] 在 sodium amalgam 作用下， 以 not given 为溶剂， 生成 [(η5-C5Me4CMe3)2Ti]
  参考文献：
  名称：

  Dinitrogen Activation by Titanium Sandwich Complexes

  摘要：

  The activation of dinitrogen by titanium sandwich complexes of the general form (eta5-C5Me4R)2Ti (R = CHMe2, CMe3, SiMe3) has been systematically investigated. Low-temperature, in situ, solution infrared spectroscopy has allowed detection of monomeric bis-dinitrogen complexes of titanium that are isostructural with more familiar dicarbonyl derivatives. One example, (eta5-C5Me4CHMe2)2Ti(N2)2, has also been characterized by X-ray diffraction and reveals weakly activated dinitrogen ligands. From the solution IR data, the relative azophilicity of the titanium sandwich complexes has been established and increases with smaller cyclopentadienyl substituents.

  DOI：

  10.1021/ja045884r

文献信息

• Decamethyltitanocene hydride intermediates in the hydrogenation of the corresponding titanocene-(η²-ethene) or (η²-alkyne) complexes and the effects of bulkier auxiliary ligands
  作者：Jiří Pinkas、Róbert Gyepes、Ivana Císařová、Jiří Kubišta、Michal Horáček、Karel Mach

  DOI：10.1039/c7dt01545c

  日期：——

  reactions of titanocene [Cp*2Ti] (Cp* = η5-C5Me5) and its derivatives [Cp*(η5:η1-C5Me4CH2)TiMe] and [Cp*2Ti(η2-CH2=CH2)] with excess dihydrogen at room temperature and pressures lower than 1 bar revealed the formation of dihydride [Cp*2TiH2] (1) and the concurrent liberation of either methane or ethane, depending on the organometallic reactant. The subsequent slow decay of 1 yielding [Cp*2TiH] (2) was mediated

  钛茂[Cp * 2Ti]（Cp * =η5-C5Me5）及其衍生物[Cp *（η5：η1-C5Me4 ）TiMe]和[Cp * 2Ti（η2-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R1 R2，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
• 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