pentamethylcyclopentadienylTi[OC(phenyl)CH] | 166111-00-8

• 英文名称: pentamethylcyclopentadienylTi[OC(phenyl)CH]
• 英文别名: bis(pentamethylcyclopentadienyl)phenyloxatitanacyclobutene；Cp*₂Ti[OC(Ph)CH]
• CAS: 166111-00-8
• 化学式: C₂₈H₃₆OTi
• 分子量: 436.473
• InChiKey: GFRNQADSKZBQNF-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：

  pentamethylcyclopentadienylTi[OC(phenyl)CH] 以 氘代甲苯 为溶剂， 生成 (C₅(CH₃)5)2Ti(OH)(CCC₆H₅)
  参考文献：
  名称：

  具有末端和内部炔烃的单体 Ti (IV) 氧代配合物的环加成和环还原反应。一种可逆的氧杂金属环丁烯/羟基乙炔相互转化

  摘要：

  Cp{sup *}{sub 2}Ti(O)(pry)的合成及结构(Cp{sup *}={eta}{sup 5}-C{sub 5}Me{sub 5};pyr=pyridine ) (1) 最近被描述。我们在此报告了 1 与末端炔烃的 [2 + 2] 环加成反应以及由此产生的氧杂金属环丁烯向羟基乙炔配合物的新型重排。至少在一种情况下，这种安排是可逆的，我们已经获得了有关其机制的信息。我们进行了旨在研究氧杂金属环到羟乙炔化物重排机制的实验。17 参考，1 图。

  DOI：

  10.1021/ja00124a036
• 作为产物：
  描述：

  、 苯乙炔 以 甲苯 为溶剂， 反应 2.0h， 以95%的产率得到pentamethylcyclopentadienylTi[OC(phenyl)CH]
  参考文献：
  名称：

  Facile C–H, C–F, C–Cl, and C–C Activation by Oxatitanacyclobutene Complexes

  摘要：

  Aryl ketones react readily with oxatitanacydobutenes bearing pentamethylcyclopentadienyl ligands to form unique titanocene complexes resulting from Cp* modification and C-H activation. An intermediate in this reaction is intercepted with various functional groups to form carbonyl insertion, C-F activation, and cyclopropane ring-opening products.

  DOI：

  10.1021/acs.organomet.5b00470

文献信息

• Synthesis, Cycloaddition, and Cycloreversion Reactions of Mononuclear Titanocene–oxo Complexes
  作者：Trang T. Nguyen、Gregory D. Kortman、Kami L. Hull

  DOI：10.1021/acs.organomet.6b00111

  日期：2016.6.13

  Titanocene-oxo complexes of the type (Cp2Ti)-Ti-x=O(L) (Cp-x = pentamethylcyclopentadienyl; tetramethylcyclopentadienyl; L = pyridine or derivatives) are synthesized from the corresponding titanocene ethylene complexes via oxidation with pyridine N-oxides or styrene oxide. These oxo complexes react with alkynes, nitriles, and alpha,beta-unsaturated carbonyls to form titanacycles, which undergo exchange reactions with Organic substrates or react with 4-dimethylaminopyridine to regenerate the titanocene oxo.: Mechanistic experiments support a dissociative mechanism in which the first step is rate-determining retrocycloaddition followed by trapping of the reactive [(Cp2Ti)-Ti-x=O] species. In the case of the retro-[4+2]-cycloaddition from dioxatitanacyclohexene complexes, a Hammett study gives rho values of -1.18 and -1.04 for substituents on two different phenyl rings on the metallacycles; suggesting positive charge buildup and a slightly asynchronous cycloreversion in the rate-determining step.