[(Ti(μ-(η5-C5Me4SiMe2O-κO)))Cl]2(μ-O) | 632353-54-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: [(Ti(μ-(η5-C5Me4SiMe2O-κO)))Cl]2(μ-O)
• 英文别名: (Ti[μ-(η5-C5Me4SiMe2O-κO)]Cl)2(μ-O)；(TiCl(μ-η5-C5Me4SiMe2O-κO))2(μ-O)；[Ti(C5Me4SiMe2O)(chloride)]2O；dimethyl-oxido-(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane;oxygen(2-);titanium(4+);dichloride
• CAS: 632353-54-9
• 化学式: C₂₂H₃₆Cl₂O₃Si₂Ti₂
• 分子量: 571.363
• InChiKey: UGSXEWHSTFBNEE-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -3.29
• 重原子数：
  31
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  47.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  [(Ti(μ-(η5-C5Me4SiMe2O-κO)))Cl]2(μ-O) 、 lithium hydroxide 以 二氯甲烷 为溶剂， 以30%的产率得到[(TiCl)(TiOH)((Ti)[μ-(η5-C5Me4SiMe2O-κO)]2(μ-O))2(μ-O)]
  参考文献：
  名称：

  合成的和新颖的四核organotitanoxane衍生物的结构表征†

  摘要：

  新颖titanoxane化合物的合成，[（的TiCl）（TiOH）{（Ti）的[μ-（η 5 -C 5我4森达2 O形κO）] 2（μ-O）} 2（μ-O）] （4）和[{钛[μ-（η 5 -C 5我4森达2 O形κO）]（μ-O）} 4 ]（5）通过双核钛氧络合物的受控反应[{钛{μ - （η 5 -C 5我4森达2 O形κO）} CL] 2（μ-O）]（1报道）与2当量的LiOH。复杂4是创新和卓越的。它是具有开放链结构的四核稳定末端羟基钛络合物的稀有实例之一，该结构与在逐步途径中提出的用于证明六核络合物[{Ti [μ- （η 5 -C 5我4森达2 O形κO）]（μ-O）} 6 ]（3从）1。1 H DOSY实验用于表征复合物4。另外，化合物5和前体1的结构通过单晶X射线衍射研究确定。

  DOI：

  10.1039/c0dt01393e
• 作为产物：
  描述：

  (Ti[μ-(η5-C5Me4SiMe2O-κO)]Cl(CH2Ph))2 在 air 作用下， 以 氘代苯 为溶剂， 生成 [(Ti(μ-(η5-C5Me4SiMe2O-κO)))Cl]2(μ-O)
  参考文献：
  名称：

  Titanium and zirconium chloro, oxo and alkyl derivatives containing silyl-cyclopentadienyl ligands. Synthesis and characterisation

  摘要：

  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.

  DOI：

  10.1016/s0022-328x(03)00430-3

文献信息

• 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.
• Stable Methylene- and Oxo-Bridged Monocyclopentadienyl Titanium Compounds. Molecular Structure of {Ti[μ-(η⁵-C₅Me₄SiMe₂-O)]Me}₂(μ-CH₂)
  作者：Olga Buitrago、Carmen Ramírez de Arellano、Gerardo Jiménez、Tomás Cuenca

  DOI：10.1021/om0495426

  日期：2004.11.1

  Thermolysis of Ti[mu-(eta(5)-C5Me4SiMe2-O)-Me-2}(2) affords the methylene-bridged titanium compound Ti[mu-(eta(5)-C5Me4SiMe2-O)]Me}(2)(mu-CH2), concurrent with the evolution of methane, the first example of a fully characterized homometallic cyclopentadienyl titanium,mu-methylene derivative. Reaction of the mu-methylene compound with water affords the isostructural U-oxo complex Ti[mu-(eta(5)-C5Me4SiMe2-O)]Me}(2)(mu-O). Reaction of the geminal dititanium methylene complex with benzophenone is also studied.