(1-(chlorodimethylsilyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride | 443889-16-5

• 英文名称: (1-(chlorodimethylsilyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride
• 英文别名: [TiCl3(η5-C5(CH3)4(Si(CH3)2Cl)]；[Ti(η5-C5Me4SiMe2Cl)Cl3]；[Ti(η5-C5H4SiMe2Cl)Cl3]；Ti(η5-C5Me4SiMe2Cl)Cl3；TiCl3(η5-C5Me4SiMe2Cl)
• CAS: 443889-16-5
• 化学式: C₁₁H₁₈Cl₄SiTi
• 分子量: 368.041
• InChiKey: CPEOAWOODGHWNI-UHFFFAOYSA-K

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：

  (1-(chlorodimethylsilyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride 、 四亚甲基二胺 以 氘代氯仿 为溶剂， 生成 [TiCl2(η5-C5Me4SiMe2-κ-N(CH2)4NH-η5-C5Me4SiMe2)TiCl3]
  参考文献：
  名称：

  Reactions of [Ti(η⁵-C₅Me₄SiMe₂Cl)Cl₃] with Diamines, a Suitable Approach to Prepare Mono- and Dinuclear Cyclopentadienyl-silyl-amido Titanium Complexes with Constrained and Unstrained Structures

  摘要：

  Complex [Ti(eta(5)-C5Me4SiMe2Cl)Cl-3] (1) reacts with NH2(CH2)(n)NH2 (n = 3, 4), under appropriate reaction conditions, to yield the corresponding di- and mononuclear constrained-geometry cydopentadienyl-silyl-amido complexes [Ti{eta(5)-C5Me4SiMe2-kappa-N(CH2)(n/2)}Cl2-](2) (n = 3, 2a; 4, 2b) and [Ti{eta(5)-C5Me4SiMe2-kappa-N(CH2)(n)NH2}Cl-2] (n = 3, 3a; 4, 3b). Complexes 2a and 2b are obtained as pure compounds when the reaction is carried out in a 1(Ti):1.5(diamine) molar ratio, while the derivatives 3 cannot be selectively prepared. Treatment of 1 with NH2(CH2)(5)NH2 gives the dinuclear derivative [Ti{eta(5)-C5Me4SiMe2-kappa-N(CH2)(2.5)-}Cl-2](2) (2c) as a single complex, regardless of the reaction stoichiometry. On monitoring these reactions by NMR spectroscopy, the formation of the transient asymmetrical dinuclear complexes [TiCl2{eta(5)-C5Me4SiMe2-kappa-N(CH2)(n)NH-eta(5)-C5Me4SiMe2}TiCl3] (n = 3, 4a; 4, 4b; 5, 4c) is observed. The analogue dinuclear complex [TiCl2{eta(5)-C5Me4SiMe2-kappa-N(CH2)(3)NMe-eta(5)-C5Me4SiMe2}TiCl3] (6) is synthesized, on a preparative scale, by treatment of 1 with an equimolar amount of N-methylpropylenediamine, which is transformed into the mononuclear derivative [Ti{eta(5)-C5Me4SiMe2-kappa-N(CH2)(3)NHMe}Cl-2] (7) upon addition of a further equivalent of the diamine. However, treatment of 1 with 1 equiv of N-methylpropylenediamine proceeds with the formation of the mononuclear constrained-geometry compound [Ti{eta(5)-CsMe4SiMe2-kappa-N(CH2)(3)NHMe center dot HCl}Cl-2] (5). The reaction of 1 with 2 equiv of NH2(CH2)(3)NMe2 or NHMe(CH2)(3)NMe2 specifically affords, respectively, a mononuclear cyclopentadienyl-silyl-amido derivative with constrained geometry, [Ti{eta(5)-C5Me4SiMe2-kappa-N(CH2)(3)NMe2}Cl-2] (8), or unconstrained geometry, [Ti{eta 5-C5Me4SiMe2NMe(CH2)(3)-kappa-NMe}Cl-2] (9). When the reaction with NHMe(CH2)(3)NHMe is monitored by NMR spectroscopy, the mononuclear intermediate [Ti{eta(5)-C5Me4SiMe2NMe(CH2)(3)NHMe}Cl-3] (11) and the dinuclear complex [Ti{eta(5)-C5Me4SiMe2NMe(CH2)(1.5)-}Cl-3](2) (12) are observed. The dinuclear complex [Ti{eta(5)-C5Me4SiMe2NMe(CH2)(3)-} Cl-3](2) (13) is synthesized by treatment of 1 with 1 equiv of NHMe(CH2)(6)NHMe. All the reported compounds were characterized

  DOI：

  10.1021/om200101k
• 作为产物：
  描述：

  1-(dimethylchlorosilyl)-1-(trimethylsilyl)-2,3,4,5-tetramethylcyclopentadiene 、 四氯化钛 以 二氯甲烷 为溶剂， 以83%的产率得到(1-(chlorodimethylsilyl)-2,3,4,5-tetramethylcyclopentadienyl)titanium trichloride
  参考文献：
  名称：

  交联的（氨基甲基）聚苯乙烯上受支持的受限几何催化剂：乙烯和1-辛烯聚合的研究

  摘要：

  TiCl 4与（氯二甲基甲硅烷基）（三甲基甲硅烷基）环戊二烯的反应导致Me 3 SiCl的化学选择性消除，并干净地得到三氯化钛（（氯二甲基甲硅烷基）环戊二烯基）钛（2）。同样地，的TiCl的反应4与（chlorodimethylsilyl）（三甲基甲硅烷）四甲基环戊二烯（6）还导致在化学选择性消除的Me 3的SiCl和干净，得到（（chlorodimethylsilyl）四甲基环戊二烯）三氯化钛（7）。该观察结果与6与ZrCl 4的反应形成鲜明对比，后者导致Me的化学选择性消除。3 SiCl，但提供了半三明治和锆茂复合物的混合物。在（氨基甲基）聚苯乙烯上的配合物2或7的载体（AMPS，1％交联，1.3 wt％N，0.928 mmol N / g载体），其中选择载体中胺含量与前体催化剂的摩尔比如果将其设为3：1，则会分别导致几何约束催化剂（CGC）8或9的组装。根据29 Si NMR，在络合

  DOI：

  10.1021/om020482i

文献信息

• Cyclopentadienyl–Silsesquioxane Titanium Complexes: Highly Active Catalysts for Epoxidation of Alkenes with Aqueous Hydrogen Peroxide
  作者：María Ventura、Marta E. G. Mosquera、Tomás Cuenca、Beatriz Royo、Gerardo Jiménez

  DOI：10.1021/ic300583g

  日期：2012.6.4

  Titanium complexes bearing an unprecedented tridentate cyclopentadienyl–silsesquioxanate ligand provide a new class of efficient and selective catalysts for epoxidation of olefins with aqueous hydrogen peroxide under homogeneous conditions.

  带有空前的三齿环戊二烯基-倍半硅氧烷配体的钛配合物为在均相条件下用过氧化氢水溶液将烯烃环氧化提供了新型的高效选择性催化剂。
• M−Cl/Si−Cl Preferential Reactivity in Chlorosilyl-Substituted Cyclopentadienyl Early Transition Metal Complexes in Reactions with Amines: Key to Understanding the Nature of the Final Product
  作者：Cristina Paniagua、Marta E. G. Mosquera、Heiko Jacobsen、Gerardo Jiménez、Tomás Cuenca

  DOI：10.1021/om9008026

  日期：2009.12.28

  The reaction of [Ti(eta(5)-C5Me4SiMe2Cl)Cl-3] (1) with 1 equiv of different ethylenediamines, NHR-(CH2)(2)NR'R '', regiospecifically affords cyclopentadienyl-silyl-amido derivatives with constrained geometry, [Tieta(5)-C5Me4SiMe2-kappa-N(CH2)(2)NR'R ''}Cl-2] (R' = R '' = H, 2a; R' = H, R '' = Me, 2b; R' = R" = Me, 2c) or unstrained structure, [Tieta(5)-C5Me4SiMe2NMe(CH)(2)-kappa-NMe)Cl-2] (3). Treatment of 1 with 1.5 equiv of ethylenediamine gives a mixture of 2a and the transient complex [Tieta(5)-C5Me4SiMe2NH(CH2)(2)NH2}Cl-3] (4), which is transformed into 2a upon addition of a base. The reaction of 1 with N,N,N'-trimethylethylenediamine permits the synthesis and isolation of the complex [Tieta(5)-C5Me4SiMe2NMe(CH2)(2)NMe2]Cl-3](5). Compound 1 reacts with 0.5 equiv of NH2(CH2)(2)NH2 to yield a mixture of 2a along with the tethered dinuclear cyclopentadienyl-silyl-amido compound [Tieta(5)-C5Me4SiMe2-kappa-N(CH2)-} Cl-2](2) (6).
• Organotitanoxanes with Unique Structure among Transition-Element Organometallic Oxide Derivatives
  作者：Olga Buitrago、Marta E. G. Mosquera、Gerardo Jiménez、Tomás Cuenca

  DOI：10.1021/ic8003646

  日期：2008.5.19

  The synthesis of novel titanoxane compounds, [(TiCl)(Ti)[mu-(eta(CMe4SiMe2O)-C-5-Me-5-kappa O)](2)(mu-O)}(2)(mu-O)] (4) and [Ti[mu-(eta(5)-(CMe4SiMe2O)-Me-5-kappa O)](mu-O)}(6)] (5), by controlled hydrolysis of a dinuclear titanium/oxo complex is described. Complexes 4 and 5 show unprecedented structural features for organometallic oxide derivatives of transition elements and represent unique fully characterized examples of tetra- and hexanuclear organo-transition-metal oxide compounds with an open-chain and a monocyclic structure, respectively.
• Reduction-Induced Cyclization and Redox Reactions of Fully Methylated Titanocene Dichlorides Bearing Pendant Alkenyldimethylsilyl Groups, [TiCl₂{η⁵-C₅Me₄(SiMe₂R)}₂] (R = Vinyl and Allyl)
  作者：Lenka Lukešová、Petr Štěpnička、Karla Fejfarová、Róbert Gyepes、Ivana Císařová、Michal Horáček、Jiří Kubišta、Karel Mach

  DOI：10.1021/om020150d

  日期：2002.6.1

  Reduction of titanocene dichlorides bearing (omega-alkenyl)dimethylsilyl substituents [TiCl2eta(5)-C5Me5(SiMe2R)}(2)], where R = CH=CH2 (3) and CH2CH=CH2 (4), affords highly reactive Ti(II) intermediates, which immediately undergo intramolecular reactions with the pendant double bonds in a way dependent on the length of the alkenyl chain. The reduction of 4 with magnesium at 60 degreesC affords cleanly the cyclopentadienyl-ring-tethered titanacyclopentane, [Ti(eta(1):eta(1):eta(5):eta(5)-C5Me4SiMe2CH(Ti)CH(Me)CH(Me)CH(Ti)SiMe2C5Me4](5), which can be opened by HCl to an ansa-titanocene dichloride with a six-membered saturated bridging chain, [TiCl2-eta:(5)eta(5)-C5Me4SiMe2CH2CH(Me)CH(Me)CH2SiMe2C5Me4)(2)}] (6). An analogous reaction of 3 can be accomplished at low temperatures and only to some extent, providing a mixture of titanacyclopentane complex [Ti(eta(1):eta(1):eta(5):eta(5)-C5Me4SiMe2CH(Ti)CH2CH2CH(Ti)SiMe2C5Me4] (10) and the fluxional eta(2)-alkene complex [Ti(eta(5)-C5Me4SiMe2CH=CH2)(eta(2):eta(5)-C5Me4SiMe2CH=CH2)1 (9). At 60 degreesC, the reduction of 3 yields a mixture of ansa-eta(2)-alkene complex [Tieta(2):eta(5)-C5Me4SiMe2CH2CH=CHCH2SiMe2C5Me4}] (7) and the product of a hydrogen loss, the doubly tethered; paramagnetic eta(3)-allyl Ti(III) complex [Tieta(3):eta(5):eta(5)-C5Me4SiMe2CHCH=CHCH2SiMe2C5Me4}] (8). When the reduction of 3 with magnesium is carried out in the presence of bis(trimethylsilyl)ethyne as the proton acceptor, 8 is obtained as the sole isolated product. Complex 8 reacts with protic reagents such as HCl and methanol under protonation/decomplexation of the allyl system to give the d(1) paramagnetic complexes [TiXeta:(5)eta(5)-C5Me4SiMe2CH2CH=CHCH2SiMe2C5Me4}] (X = Cl, 12; OMe, 13). Oxidation of 8 with PbCl2 yields eta(1)-alkenyl complex [TiCleta(1):eta(5):eta5-C5Me4SiMe2CH(Ti)CH=CHCH2SiMe2C5Me4}] (11). A similar oxidation of 12 to ansa-titanocene dichloride [TiCl2eta:(5)eta-C5Me4SiMe2CHCH=CHCH2SiMe2C5Me4}] (14) containing a symmetrical unsaturated bridging chain requires a stronger oxidizing agent, AgCl. Compounds 5, 7, 8, and 10-14 have been characterized by X-ray crystallography.
• Titanium and zirconium chloro, oxo and alkyl derivatives containing silyl-cyclopentadienyl ligands. Synthesis and characterisation
  作者：Olga Buitrago、Gerardo Jiménez、Tomás Cuenca

  DOI：10.1016/s0022-328x(03)00430-3

  日期：2003.10

  The reaction of the tetramethylcyclopentadiene-silyl substituted derivative C5Me4(SiMe3)(SiMe2Cl) with MCl4 afforded the trichloro mono-tetramethylcyclopentadienyl complexes M(eta(5)-C5Me4SiMe2Cl)Cl-3 [M = Ti (1), Zr (2)] with selective elimination of SiMe3Cl. Compound 1 reacts with deoxygenated water in methylene chloride, with the evolution of HCl, to give the dinuclear titanium compound Ti[mu-(eta(5)-C5Me4SiMe2O-kappaO)]Cl-2}(2) (3), which was converted into the mu-oxo complex Ti[mu-(eta(5)-C5MC4SiMe2O-kappaO)]Cl}(2)(mu-O) (4) by a further hydrolysis reaction which occurred when a solution of 3 in toluene was refluxed for a long period of time in the air. Depending on the size of the alkyl ligand, reactions of the mononuclear compound 1 with an appropriate alkylating reagent rendered the peralkylated Ti(eta(5)-C5Me4SiMe2R)R-3 [R = Me (5), CH2Ph (6)] or partially alkylated Ti[(eta(5)-C5Me4SiMe2(CH2SiMe3)]Cl(CH2SiMe3)(2)} (7) compounds by a salt metathesis route. Attempts to synthesise a partially methylated or benzylated complex were unsuccessful. Treatment of the dinuclear compound 3 with four equivalents of MgClMe yielded the tetramethyl derivative Ti[mu-(eta(5)-C5Me4SiMe2O-KO)]Me-2}(2) (8), while the same reaction carried out with MgCl(CH2Ph) or Mg(CH2Ph)(2).2THF gave the chloro-benzyl derivative Ti[mu-(eta(5)-C5Me4SiMe2O-kappaO)]Cl(CH2Ph)}(2) (9) as an equimolar mixture of diastereomers, regardless of the molar ratio of the alkylating reagent used. All of the new compounds were characterised by elemental analysis and NMR spectroscopy. (C) 2003 Elsevier B.V. All rights reserved.