((cyclohexyl)2N)3TiCl | 187390-26-7

• 英文名称: ((cyclohexyl)2N)3TiCl
• 英文别名: ClTi(NCy2)₃；ClTi(dicyclohexylamido)₃；(Cy₂N)₃TiCl；((cyclohexyl)₂N)₃TiCl；tris(dicyclohexylamido)titanium chloride
• CAS: 187390-26-7
• 化学式: C₃₆H₆₆ClN₃Ti
• 分子量: 624.273
• InChiKey: PPAQGFPHCWEAFV-UHFFFAOYSA-M

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：

  ((cyclohexyl)2N)3TiCl 以 正己烷 为溶剂， 反应 5.0h， 生成 [(dicyclohexylamido)₂Ti(NCy)]₂
  参考文献：
  名称：

  Remarkably Robust Mono-n-butyl Group IV Dicyclohexylamido Complexes {(Cy)₂N}₃M(n-butyl) (Cy: cyclohexyl [C₆H₁₁], M: Ti, Zr)

  摘要：

  The syntheses of alkyl titanium and zirconium dicyclohexylamido complexes from (Cy2N)(3)MCl (Cy: cyclohexyl, M: Ti 1a, M: Zr 1b) are presented. Particularly the beta-H-containing n-butyl derivatives (Cy2N)(3)(MBu)-Bu-n (M: Ti 3a, M: Zr 3b) become available as isolable, thermally stable complexes by reactions of 1 with n-BuLi. The solid-state structures of 3a and 3b are presented. No hints for C-H agostic interactions are found. The behavior of 3 is discussed in comparison to the corresponding methyl complexes (Cy2N)(3)MMe (M: Ti 2a, M: Zr 2b) in the solid state, as well as in solution.

  DOI：

  10.1021/om5008105
• 作为产物：
  描述：

  tetrachlorobis(tetrahydrofuran)titanium(IV) 、 lithium dicyclohexylamide 以 正戊烷 为溶剂， 以72%的产率得到((cyclohexyl)2N)3TiCl
  参考文献：
  名称：

  三（二环己基氨基）钛和氯化锆的合成及（c-Hex2N）3TiCl的结构

  摘要：

  摘要MCl 4（THF）2（M-Ti和Zr）与过量LiNCy 2在戊烷中的反应可产生结晶（c-Hex 2 N）3 MCl，产率超过70％。产物通过1 H，13 C，1 H和13 C HETCOR NMR和MS技术表征。晶体（c-Hex 2 N）3 TiCl的特征还在于单晶X射线结构。注意到了（R 2 N）3 TiCl的结构尺寸的趋势。

  DOI：

  10.1016/0277-5387(96)00324-5

文献信息

• Bulky Titanium Amides: C–H Bond Activation under Mild Conditions
  作者：Christian Adler、Alexander Bekurdts、Detlev Haase、Wolfgang Saak、Marc Schmidtmann、Rüdiger Beckhaus

  DOI：10.1002/ejic.201400022

  日期：2014.3

  metathesis reactions initiates a spontaneous C–H activation at room temperature. The titanaaziridine (η5‐CpAd)(η2‐NCy2)TiNCy2 (9) formed after a β‐C–H activation with LiNCy2. The use of NaN(SiMe3)2 results in a γ‐C–H activation and the formation of the azatitanacyclobutane (10). The alkylation of ClTi(NCy2)3 (7) with methyllithium produces the reactive complex MeTi(NCy2)3 (11). The spontaneous reaction of

  由TiCl 4和二环己胺（Cy 2 NH）合成了庞大的钛单酰胺配合物Cl 3 TiNCy 2（1）。的固态结构1展示了金属中心和一个之间的紧密接触的分子内本位酰氨配体的碳原子上。该接触可以表明类似于过渡金属烷基化合物的有害相互作用。的配位球的改变1与中性配体[吡啶（2），2,2'-联吡啶（3），Ñ，Ñ，N' ，N'-四甲基乙烷-1，2-二胺（tmeda，4）和1,2-双（二甲基膦基）乙烷（dmpe，5）]产生具有配体子午线排列的八面体化合物。的固态结构5揭示了钛原子和一之间的显著更紧密的接触本位配体的碳原子上。的镁还原1在adamantylidenepentafulvene的存在产生了深绿色的复合物（η 5，η 1 -adamantylidenepentafulvene）的Ti（NCY 2）氯（8）。最后一个氯原子与其他庞大的酰胺配体[NCy 2，N（SiMe 3）2的交换通过盐复分解反应
• Tris(dicyclohexylamido) Group 4 Metal Allyl and Phenylacetylide Complexes – Synthesis and Characterization
  作者：Nils Frerichs、Lenard Lukas、Marc Schmidtmann、Rüdiger Beckhaus

  DOI：10.1002/ejic.202000682

  日期：2020.12.7

  The synthesis and characterization of organyl complexes derived from group 4 metal dicyclohexylamido complexes (Cy2N)3MCl (Cy: Cyclohexyl, M = Ti, Zr, Hf 1‐M) is presented. The allyl Grignard reagent is used to obtain the corresponding group 4 allyl complexes 2‐M, and lithium phenylacetylide is used to obtain the phenylacetylide complexes 3‐M. The thermal stability of complexes 2‐M and 3‐M is investigated

  介绍了合成和表征衍生自第4组金属双环己基酰胺基复合物（Cy 2 N）3 MCl（Cy：环己基，M = Ti，Zr，Hf 1-M）的有机基复合物。烯丙基格利雅试剂用于获得相应的4组烯丙基配合物2-M，苯乙炔化锂用于获得苯乙炔配合物3-M。研究了配合物2-M和3-M的热稳定性。所有络合物均通过NMR光谱和X射线单晶衍射表征。讨论了它们在溶液和固态中的分子结构。
• Zwitterionic d⁰ Metal Complexes [(Cy₂N)₃M]⁺[(μ-Me)B(C₆F₅)₃]⁻ (M = Ti, Zr, Hf) Derived from Tris(dicyclohexylamido)methyl Metal Precursors
  作者：Christian Adler、Nils Frerichs、Marc Schmidtmann、Rüdiger Beckhaus

  DOI：10.1021/acs.organomet.6b00688

  日期：2016.11.14

  The synthesis and characterization of tris(dicyclohexyl)amido hafnium complexes ClHf(NCy2)(3) (1-Hf) and MeHf(NCy2)(3) (2-Hf) are presented. The reactions of the group 4 derivatives of this compound class (MeM(NCy2)(3); M = Ti (2-Ti), Zr (2-Zr), Hf (2-Hf)) with B(C6F5)(3) are investigated. Their reactions with strong Lewis acids lead to the first examples of zwitterionic group 4 complexes employing three amido ligands at the electrophilic metal center ([(Cy2N)(3)M](+)[(mu-Me)B(C6F5)(3)](-)). The solid-state structures of all of the betaines (3-Ti, 3-Zr, 3-Hf) are presented and compared. In all homologues the methyl group is abstracted by the Lewis acid but remains in interaction with the electron-deficient metal center, resulting in a linearly bridging methyl group. The M center dot center dot center dot C distances of 3-M are elongated by 0.25 angstrom (av) in comparison to 2-M.