[(η(5)-C5Me4(SiMe3))2Ti] | 1173710-58-1

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: [(η(5)-C5Me4(SiMe3))2Ti]
• 英文别名: titanium(2+);trimethyl-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane
• CAS: 1173710-58-1
• 化学式: C₂₄H₄₂Si₂Ti
• 分子量: 434.648
• InChiKey: XYCKUKJUUKSEIU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.37
• 重原子数：
  27
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [(η(5)-C5Me4(SiMe3))2Ti] 以 甲苯 为溶剂， 以65%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：

  (η2-bis(trimethylsilyl)ethyne)bis(η5-tetramethyl(trimethylsilyl)cyclopentadienyl)titanium(II) 以 neat (no solvent, solid phase) 为溶剂， 生成 [(η(5)-C5Me4(SiMe3))2Ti]
  参考文献：
  名称：

  双[η 5 -四甲基（三甲基硅基）环戊二烯基]合钛（II）及其π-配合物的双（三甲基甲硅烷基）乙炔和乙烯

  摘要：

  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。

  DOI：

  10.1021/om990286k
• 作为试剂：
  描述：

  氮 、 在 [(η(5)-C5Me4(SiMe3))2Ti] 作用下， 以 苯 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 生成
  参考文献：
  名称：

  Four-Coordinate Fe N₂ and Imido Complexes Supported by a Hemilabile NNC Heteroscorpionate Ligand

  摘要：

  DOI：

  10.1021/acs.inorgchem.2c01656

文献信息

• Catalytic Proton Coupled Electron Transfer from Metal Hydrides to Titanocene Amides, Hydrazides and Imides: Determination of Thermodynamic Parameters Relevant to Nitrogen Fixation
  作者：Iraklis Pappas、Paul J. Chirik

  DOI：10.1021/jacs.6b08009

  日期：2016.10.12

  bis(cyclopentadienyl) titanium amides, hydrazides and imides by proton coupled electron transfer (PCET) is described. Twelve different N-H bond dissociation free energies (BDFEs) among the various nitrogen-containing ligands were measured or calculated, and effects of metal oxidation state and N-ligand substituent were determined. Two metal hydride complexes, (η5-C5Me5)(py-Ph)Rh-H (py-Ph = 2-pyridylphenyl

  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
• Dinitrogen Complexes of Bis(cyclopentadienyl) Titanium Derivatives: Structural Diversity Arising from Substituent Manipulation
  作者：Tamara E. Hanna、Emil Lobkovsky、Paul J. Chirik

  DOI：10.1021/om900282u

  日期：2009.7.27

  family of bis(cyclopentadienyl)titanium sandwich complexes, (η5-C5Me4R)2Ti (R = alkyl, aryl, silyl), has been systematically evaluated by in situ solution infrared spectroscopy. The maximum temperature of N2 coordination (Tmax) has been determined as a function of cyclopentadienyl substituent and has been correlated with the structural type (monomer or dimer) of the resulting dinitrogen complex. The electronic

  二氮协调到一个家庭双（环戊二烯基）钛的夹心复合，（η的5 -C 5我4 R）2的Ti（R =烷基，芳基，甲硅烷基），进行了系统的原位溶液评价红外光谱。已经确定了N 2配位的最高温度（T max）是环戊二烯基取代基的函数，并且已与所得二氮配合物的结构类型（单体或二聚体）相关。每个钛夹心复合物的电子特性是由二羰基衍生物的红外光谱，并通过相应的二茂铁的氧化电位进行评估，（η 5 -C 5Me 4 R）2 Fe。根据这些数据，已经确定了N 2配位的热力学偏好，并且随着较小的正电取代基的增加而增加。
• N–H Group Transfer and Oxidative Addition Chemistry Promoted by Isolable Bis(cyclopentadienyl)titanium Sandwich Complexes
  作者：Tamara E. Hanna、Emil Lobkovsky、Paul J. Chirik

  DOI：10.1002/ejic.200601134

  日期：2007.6

  (2-methylaziridine) to the bis(cyclopentadienyl)titanium sandwich complexes, (η5-C5Me4R)2Ti (R = iPr, SiMe3), resulted in rapid [NH] group transfer followed by C–H activation of a cyclopentadienyl methyl group to yield the corresponding cyclometalated titanocene amido compounds. Exposure of these molecules to 4 atm of H2 at 55 °C resulted in hydrogenolysis of the metal–carbon bond to form the titanium amido hydride compounds

  将丙烯亚胺（2-甲基氮丙啶）添加到双（环戊二烯基）钛夹心复合物（η5-C5Me4R）2Ti（R = iPr，SiMe3）中，导致快速的 [NH] 基团转移，然后是环戊二烯基甲基的 C-H 活化生成相应的环金属化二茂钛酰胺化合物。这些分子在 55°C 下暴露于 4 个大气压的 H2 导致金属-碳键氢解，形成钛酰氨基氢化物化合物 (η5-C5Me4R)2Ti(NH2)H。用 DCl 气体氘化证实了从与异丙基和三甲基甲硅烷基取代基相邻的位置进行的排他性环金属化。还观察到胺的 N-H 键的氧化加成。将 NH3 添加到 (η5-C5Me4SiMe3)2Ti 或 (η5-C5Me4iPr)2Ti 中产生相应的二茂钛酰胺氢化物以及二茂钛 (III) 酰胺，
• 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
• Dihydrogen and Silane Addition to Base-Free, Monomeric Bis(cyclopentadienyl)titanium Oxides
  作者：Tamara E. Hanna、Emil Lobkovsky、Paul J. Chirik

  DOI：10.1021/ic070205+

  日期：2007.4.1

  Synthesis of a family of monomeric, base-free bis(cyclopentadienyl)titanium oxide complexes, (eta5-C5Me4R)2Ti=O (R = iPr, SiMe3, SiMe2Ph), has been accomplished by deoxygenation of styrene oxide by the corresponding sandwich compound. One example, (eta5-C5Me4SiMe2Ph)2Ti=O, was characterized by X-ray diffraction. All three complexes undergo clean and facile hydrogenation at 23 degrees C, yielding the

  已通过相应的夹心化合物对苯乙烯氧化物进行脱氧，完成了一系列单体，无碱的双（环戊二烯基）钛氧化物配合物（eta5-C5Me4R）2Ti = O（R = iPr，SiMe3，SiMe2Ph）的合成。一个实例，（eta5-C5Me4SiMe2Ph）2Ti ＝ O，通过X射线衍射表征。所有这三种配合物均在23°C下进行清洁且容易的氢化反应，生成钛茂烃羟基氢化物配合物（eta5-C5Me4R）2Ti（OH）H。对于（eta5-C5Me4SiMe3）2Ti = O，氢化动力学在二氢中是一级的，并且在23°C时具有2.7（3）的正态一级动力学同位素效应，与1,2-加成途径一致。对于硅烷添加，确定了相同方向但幅度较小的同位素效应。