Ti(η(5)-C5H4SiMe2Cl)Cl3 | 159771-53-6

• 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: Ti(η(5)-C5H4SiMe2Cl)Cl3
• 英文别名: chloro-cyclopenta-1,4-dien-1-yl-dimethylsilane;trichlorotitanium(1+)
• CAS: 159771-53-6
• 化学式: C₇H₁₀Cl₄SiTi
• 分子量: 311.934
• InChiKey: XFNAEOCUEVNDHE-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：

  Ti(η(5)-C5H4SiMe2Cl)Cl3 、 叔丁胺 在 NEt₃ 作用下， 以 正己烷 为溶剂， 以63%的产率得到(η(5):η(1)-C5H4SiMe2N(t)Bu)TiCl2
  参考文献：
  名称：

  [（酰胺基甲硅烷基）环戊二烯基]钛和-锆配合物的合成和反应性。的透视分子结构中，[Zr {η 5：η 1 -C 5 ħ 4森达2（μ-O）}氯2 {H 2 N（CHME）PH}] 2 †

  摘要：

  钛（IV）和锆（IV）的新型半夹心（amidosilyl）环戊二烯基复合物从氯代甲硅烷基取代的环戊二烯基前体的合成[M（η 5 -C 5 H ^ 4森达2 Cl）的氯3 ]（M =的Ti（1a），Zr（1b））。钛[Ti（η的反应5 -C 5 H ^ 4森达2 Cl）的氯3 ]（1A）与LiNHR净的存在3给出了钛[Ti（η 5：η 1 -C 5 ħ 4森达2 NR）氯2]（R = t Bu（2a），（±）-CH（Me）Ph（3a））络合物。类似地，加入2当量的LiN（森达的3）2至复杂1A，得到二酰胺衍生物钛[Ti（η 5 -C 5 H ^ 4森达2 Cl）的氯{N（森达3）2 } 2 ] （图4a）。所述amidotitanium复杂钛[Ti（η 5：η 1 -C 5 ħ 4森达2 NH吨丁基）氯2（NH吨丁基）] （5a）中通过使1a与NH 2 t Bu以1：3的摩尔比反应以低收率制

  DOI：

  10.1021/om960606p
• 作为产物：
  描述：

  [Ti(η⁵-C5H4SiMe2OMe)Cl3] 以 氘代氯仿 为溶剂， 生成 Ti(η(5)-C5H4SiMe2Cl)Cl3
  参考文献：
  名称：

  Synthesis, characterization and styrene polymerization behavior of alkoxysilyl-substituted monocyclopentadienyltitanium(IV) complexes

  摘要：

  Trimethylsilylcyclopentadienes bearing alkoxysilyl functionality, C5H4(SiMe3)(SiMe2OR), where R is Me (2), i-Pr (3) and t-Bu (4), were prepared and characterized. Methoxy derivative 2 reacts with TiCl4 giving unstable [Ti(eta(5)-C5H4SiMe2OMe)Cl-3] (5), which is slowly transformed to chlorosilyl complex [Ti(eta(5)-C5H4SiMe2Cl)Cl-3] (6) and a mixture of cyclopentadienyltitanium(IV) methoxides on heating. Fully alkoxylated derivatives of the type [Ti(eta(5)-C5H4SiMe2OR)(OR)(3)] [R = Me (7), i-Pr (8), t-Bu (9)] and {Ti[eta(5)-C5H4SiMe(OMe)(2)](OMe)(3)} (10), were synthesized in low-to-moderate yields from respective chlorosilylcyclopentadienyltitanium trichlorides. All prepared alkoxysilyl compounds were characterized by spectroscopic techniques including Si-29 NMR. Polymerization activity of 7-10 in the presence of methylaluminoxane was determined and compared with [TiCp(OMe)(3)] and corresponding trimethylsilyl-substituted compounds [Ti(eta(5)-C5H4SiMe3)(OR)(3)], where R is Me, i-Pr and t-Bu. The highest conversion of styrene has been observed in systems based on [Ti(eta(5)-C5H4SiMe3)(OMe)(3)], [TiCp(OMe)(3)] and [Ti(eta(5)-C5H4SiMe3)(OBut)(3)], respectively. The new alkoxysilyl compounds 7-10 have significantly lower activity of 500-1800 kg of polystyrene/(mol Ti mol styrene h). All prepared polystyrenes showed both high melting point and high degree of syndiotacticity as determined by DSC and NMR measurements. (C) 2012 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2012.11.040

文献信息

• Monocyclopentadienyl Phenoxido–Amino and Phenoxido–Amido Titanium Complexes: Synthesis, Characterisation, and Reactivity of Asymmetric Metal Centre Derivatives
  作者：Giuseppe Alesso、Martial Sanz、Marta E. G. Mosquera、Tomás Cuenca

  DOI：10.1002/ejic.200800553

  日期：2008.10

  /ethyl ether solution. The reaction of TiCpCl 3 with 2a in the presence of 2.5 equiv. of NEt 3 in a polar solvent (thf, CH 2 Cl 2 or toluene) at room temperature affords TiCp[Ph(H)NCH2(3,5-tBu 2 C 6 H 2 -2-O)]Cl (6a) as a mixture of two stereoisomers. All the reported compounds were characterised by the usual analytical and spectroscopic methods and the molecular structures of 2a, 2d, 2e and 3d were

  酚亚胺衍生物的还原 R'N=CH(3,5-R 2 C 6 H 2 -2-OH) (R = tBu; R' = C 6 H 5 la, p-MeC 6 H 4 1b, Cy 1c, tBu 1d, 2,6-Me 2 C 6 H 3 1e；R = H；R' = p-MeC 6 H 4 1f；Cy = 环己基）与 MBH 4 (M = Li, Na) 或 AlLiH 4 in乙醚或 thf 在室温下得到苯酚-胺化合物 R'NHCH2(3,5-R2C 6 H 2 -2-OH) 2a-c 和 2e,f。NR-[2,4-二-叔丁基]苯并-1-oxa-3-azine物质（R = tBu 2dl, 2,6-Me 2 C 6 H 3 2el）通过2的曼尼希反应获得， 4-二叔丁基苯酚与 RNH 2 在回流甲醇中。中间体2dl在室温下在乙醇中转化为N-叔丁基[2-羟基-3,5-二-叔丁基]苄胺(2d)，而2e
• Selective sulfoxidation with hydrogen peroxide catalysed by a titanium catalyst
  作者：Lorena Postigo、Maria Ventura、Tomás Cuenca、Gerardo Jiménez、Beatriz Royo

  DOI：10.1039/c4cy00965g

  日期：——

  A cyclopentadienyl–silsesquioxane titanium complex efficiently catalyses the selective oxidation of sulfides to sulfoxides (85–98% yield in 5 min at ambient temperature) and sulfones with near-stochiometric amount of aqueous H₂O₂ in methanol.

  一个环戊二烯基-硅倍半氧钛配合物有效地催化了亚硫酸盐的选择性氧化为亚砜（在甲醇中，在室温下5分钟内产率为85-98%），并且使用接近化学计量的水合过氧化氢氧化为砜。
• Synthetic and reactivity studies of mono- and dicyclopentadienyl titanium, zirconium and hafnium complexes with the chlorodimethylsilyl-cyclopentadienyl ligand. X-ray molecular structure of Hf{(η5-C5H4)SiMe2OSiMe2(η5-C5H4)}Cl2 and Zr(η5-1,3-tBu2C5H3)(η5-C5H4SiMe2-η-NtBu)Cl
  作者：Santiago Ciruelos、Alfredo Sebastián、Tomás Cuenca、Pilar Gómez-Sal、Antonio Manzanero、Pascual Royo

  DOI：10.1016/s0022-328x(00)00213-8

  日期：2000.6

  Reaction of the disilylated cyclopentadiene C5H4(SiClMe2)(SiMe3) with HfCl4, in heptane, gave the monocyclopentadienyl complex Hf(η5-C5H4SiClMe2)Cl3 (1c). Addition of two equivalents of C5H5(SiClMe2) to a solution of MCl4, in toluene under reflux and in the presence of two equivalents of NEt3, afforded the dichloro derivatives M(η5-C5H4SiClMe2)2Cl2 [M=Ti (2a), Hf (2c)]. Compounds 2a and 2c react with a

  的二甲硅烷基化的环戊二烯的C反应5 ħ 4（SiClMe 2）（森达3）用的HfCl 4，在庚烷中，得到单环戊二烯基络合物的Hf（η 5 -C 5 H ^ 4 SiClMe 2）氯3（1C）。的C两个当量的另外5 ħ 5（SiClMe 2）到的MC1中的溶液4在回流下和在网的两个当量的存在下，在甲苯3，得到二氯衍生物M（η 5 -C 5 H ^ 4 SiClMe2）2 Cl 2 [M ＝ Ti（2a），Hf（2c）]。化合物2A和2C与水与SiCl键的选择性水解的化学计量量的反应，得到四甲基二硅氧烷桥连络合物diciclopentadienylμ（η 5 -C 5 H ^ 4）森达2 OSiMe 2（η 5 -C 5 H ^ 4）} Cl 2 [M ＝ Ti（3a），Hf（3c）]。三氯金属的化合物反应M（η 5 -C 5 H ^ 4SiClMe 2）氯3与铊（1,3-吨卜2 ç 5 ħ
• A Versatile Synthetic Route for Cyclopentadienyl−Amido Titanium(IV) Compounds. NMR Spectroscopy Study and X-ray Molecular Structure of [Ti{η⁵-C₅H₄SiMe₂NMe(CH₂)₂-η-NMe}Cl₂]
  作者：Gerardo Jiménez、Esteban Rodríguez、Pilar Gómez-Sal、Pascual Royo、Tomás Cuenca、Mikhail Galakhov

  DOI：10.1021/om000950t

  日期：2001.6.1

  presence of 2 equiv of NEt3 gave a mixture of two complexes, [Tiη5-C5H4SiMe2NMe(CH2)2-η-NMe}Cl2] (1) and [Tiη5-C5H4SiMe2-η-N(CH2)2-η-NHMe}Cl2] (2), in a molar ratio of 3:1. However, a similar reaction with N-methylethylenediamine afforded complex 2 regiospecifically. The dialkyl derivatives [Tiη5-C5H4SiMe2NMe(CH2)2-η-NMe}R2] (R = Me (3), CH2Ph (4)) were prepared by reacting the dichloride complex 1 with

  的氯代甲硅烷基取代的环戊二烯基化合物的反应钛[Ti（η 5 -C 5 H ^ 4森达2 Cl）的氯3 ]与Ñ，Ñ “在2当量网的存在二甲基乙二胺3给予了两种配合物的混合物，[钛η 5 -C 5 H ^ 4森达2 NME（CH 2）2 -η-NME}氯2 ]（1）和钛[Ti η 5 -C 5 H ^ 4森达2 -η-N（CH 2）2-η-NHMe} Cl 2 ]（2），摩尔比为3：1。然而，与N-甲基乙二胺的类似反应在区域特异性上提供了复合物2。二烷基衍生物钛[Ti η 5 -C 5 H ^ 4森达2 NME（CH 2）2 -η-NME} - [R 2 ]（R =我（3），CH 2 Ph（上4））由二氯化物反应制备配合物1分别具有2当量的MgClMe或1当量的Mg（CH 2 Ph）2 ·2THF。与LiNMe 2的类似反应得到二酰胺衍生物钛[Ti η 5 -C 5 H ^ 4森达2 NME（CH
• Synthesis, Characterization, and Reactivity of Niobium and Tantalum Complexes Bearing Metal−Nitrogen Bonds. X-ray Molecular Structure of [Nb(C₅H₄SiMe₃){NH(CH₂)₂-η-NH₂}Cl₃] and the Novel Tetranuclear Niobium Oxo Derivative [{Nb(C₅H₄SiMe₃)Cl(μ₂-O)}₄(Cl)₂(μ₃-O)]
  作者：M. Carmen Maestre、Cristina Paniagua、Eberhardt Herdtweck、Marta E. G. Mosquera、Gerardo Jiménez、Tomás Cuenca

  DOI：10.1021/om7002927

  日期：2007.8.1

  three-component mixture, the chlorosilyl-substituted cyclopentadienyl titanium compound [Ti(η5-C5H4SiMe2Cl)Cl3], the corresponding mononuclear amido-amino, [NbCpRNH(CH2)2-η-NH2}Cl3] (CpR = Cp‘, 4a; Cp*, 4b), and the dinuclear imido niobium complexes [NbCpRCl2}2(μ-N(CH2)2-η-N)] (CpR = Cp‘, 5a; Cp*, 5b). In contrast, the analogue tantalum complexes thermally degraded, when CpR = Cp‘ at normal temperature, whereas

  环戊二烯基甲硅烷基酰氨基钛化合物的反应钛[Ti η 5 -C 5 H ^ 4森达2 -η-N（CH 2）2 -η-NH 2 }氯2 ]与第5种族金属的单环戊二烯配合物[MCP ř CL 4 ];（M =铌，钽的CP - [R = C 5 H ^ 4森达3（CP'），C 5我5，得到（CP *））双核配合物[的TiCl 2 η 5 -C 5 H ^ 4森达2 -η-N（CH 2）2 -κ-NH 2 } MCP ř氯4 ]（M =铌中，CP [R = CP ' 2a中; *的CP，2B ; M =钽中，CP [R = CP'，3A ; CP =的CP *，3B） 。化合物2演变在室温下，得到的三组分混合物中，氯甲硅烷取代的环戊二烯钛化合物钛[Ti（η 5 -C 5 H ^ 4森达2 Cl）的氯3 ]，相应的单核酰氨基-氨基，[国家预防腐败局ř NH（CH 2）2 -η-NH 2 }氯3