[TiCl2(η5-C5Me4SiMe3)2] | 185154-26-1

• 英文名称: [TiCl2(η5-C5Me4SiMe3)2]
• 英文别名: bis(η5-tetramethyl(trimethylsilyl)cyclopentadienyl)titanium dichloride；((trimethylsilyl)tetramethylcyclopentadienyl)2TiCl2；[TiCl₂(η⁵-C₅Me₄SiMe₃)₂]；(η⁵-C₅Me₄SiMe₃)₂TiCl₂；TiCl2[C5Me4(SiMe3)]2
• CAS: 185154-26-1
• 化学式: C₂₄H₄₂Cl₂Si₂Ti
• 分子量: 505.554
• InChiKey: MMLQDBDMDAECAT-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-C5Me4SiMe3)2] 、 甲基锂 以 正己烷 为溶剂， 以87%的产率得到dimethylbis(η5-tetramethyl(trimethylsilyl)cyclopentadienyl)titanium(IV)
  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：

  (η⁵-C₅Me₄SiMe₃)₂Ti(Cl)(NHN(CH₃)₂) 在 (η5-C5Me5)Cr(CO)3H 作用下， 以 氘代苯 为溶剂， 反应 2.0h， 以0.040 mmol的产率得到[TiCl2(η5-C5Me4SiMe3)2]
  参考文献：
  名称：

  从金属氢化物到茂钛酰胺、酰肼和酰亚胺的催化质子耦合电子转移：与固氮相关的热力学参数的测定

  摘要：

  描述了通过质子耦合电子转移 (PCET) 氢解一系列双（环戊二烯基）钛酰胺、酰肼和酰亚胺中的钛 - 氮键。测量或计算了各种含氮配体之间 12 种不同的 NH 键解离自由能 (BDFE)，并确定了金属氧化态和 N-配体取代基的影响。两种金属氢化物络合物，(η5-C5Me5)(py-Ph)Rh-H (py-Ph = 2-吡啶基苯基，[Rh]-H) 和 (η5-C5R5)(CO)3Cr-H ([Cr]RH , R= H, Me) 被评估为正式的 H 原子转移反应性，并因其相对较弱的 MH 键强度但能够激活和裂解分子氢而被选中。尽管具有可比性的 MH BDFE，观察到两种化合物之间不同的反应性，这可以追溯到 MH 键的极大不同酸度和分子的整体氧化还原电位。使用 [Rh]-H，使用 H2 作为化学计量的 H 原子源，从相应的钛 (IV) 配合物完成了氨、甲硅烷基胺和 N,N-二甲基肼的催化合成。本研

  DOI：

  10.1021/jacs.6b08009

文献信息

• Ammonia Synthesis by Hydrogenolysis of Titanium–Nitrogen Bonds Using Proton Coupled Electron Transfer
  作者：Iraklis Pappas、Paul J. Chirik

  DOI：10.1021/jacs.5b01047

  日期：2015.3.18

  The catalytic hydrogenolysis of the titanium-amide bond in (η(5)-C5Me4SiMe3)2Ti(Cl)NH2 to yield free ammonia is described. The rhodium hydride, (η(5)-C5Me5)(py-Ph)RhH (py-Ph = 2-phenylpyridine), serves as the catalyst and promotes N-H bond formation via hydrogen atom transfer. The N-H bond dissociation free energies of ammonia ligands have also been determined for titanocene and zirconocene complexes

  描述了 (η(5)-C5Me4SiMe3)2Ti(Cl)NH2 中钛-酰胺键的催化氢解以产生游离氨。氢化铑 (η(5)-C5Me5)(py-Ph)RhH（py-Ph = 2-苯基吡啶）作为催化剂，通过氢原子转移促进 NH 键的形成。还测定了二茂钛和二茂锆配合物的氨配体的 NH 键解离自由能，并揭示了对金属特性和氧化态的明显依赖性。在所有情况下，配位 NH3 的 NH BDFE 比游离气相分子中的值降低了 >40 kcal/mol。
• 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
• 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。
• Effects of substituents in cyclopentadienyltitanium trichlorides on electronic absorption and 47,49Ti NMR spectra and styrene polymerization activated by methylalumoxane
  作者：Jiří Pinkas、Antonín Lyčka、Pavel Šindelář、Róbert Gyepes、Vojtech Varga、Jiří Kubišta、Michal Horáček、Karel Mach

  DOI：10.1016/j.molcata.2006.05.016

  日期：2006.9

  In the series of the methylated compounds (η5-C5H5−nMen)TiCl3 (n = 0–5) 1–6, linear correlations of λmax of the absorption band and δ49,47Ti chemical shift with the number of Me groups were found. It is due to the dependence of both the magnitudes on the HOMO–LUMO energy gap which is influenced by electron donating methyl substituents. The catalysts made by combining 1–6 with MAO (molar ratio Al/Ti

  该系列中的甲基化的化合物的（η 5 -C 5 H ^ 5- Ñ我Ñ）的TiCl 3（Ñ  = 0-5）1 - 6，的线性关系λ最大的吸收带的和δ 49,47的Ti的化学位移与我组的数量被发现。这是由于这两个幅度都依赖于受电子给体甲基取代基影响的HOMO-LUMO能隙。结合1 – 6制成的催化剂MAO（Al / Ti 500的摩尔比）仅显示出活性下降与甲基数目的总体依赖性。对于化合物（η 5 -C 5我4 R）的TiCl 3 7 - 14和（η 5 -C 5 H（1,2,3-）Me 3 R）的TiCl 3 15 - 20，其中R =烷基，甲硅烷基或苯基没有之间的相关性λ最大和δ被发现。进行了有限的DFT计算，以分配所涉及的HOMO / LUMO轨道。16和20的晶体结构被确定，并进行了其他检查，以证明不存在位阻。光谱性质与催化活性的不良相关性不足为奇，这是因为通常预期到环戊二烯基配体在阳离子聚合中心的空间效应。
• 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.