(κ3-O,C,O-{(3,5-t-Bu2-C6H2O)2N2C3H4})HfCl(CH2Ph) | 1380579-92-9

• 英文名称: (κ3-O,C,O-{(3,5-t-Bu2-C6H2O)2N2C3H4})HfCl(CH2Ph)
• 英文别名: (κ³-O,C,O-{(3,5-t-Bu₂-C₆H₂O)₂N₂C₃H₄})HfCl(CH₂Ph)
• CAS: 1380579-92-9
• 化学式: C₃₈H₅₁ClHfN₂O₂
• 分子量: 781.778
• InChiKey: LJYUEKIVYGKMLM-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：

  四氢呋喃 、 (κ3-O,C,O-{(3,5-t-Bu2-C6H2O)2N2C3H4})HfCl(CH2Ph) 以 二氯甲烷-D2 为溶剂， 生成
  参考文献：
  名称：

  含NHC的第4组金属螯合物中异常的苄基迁移反应性：合成，表征和机理研究。

  摘要：

  The reaction of 1 equiv of [M(CH2Ph)(4)] (M = Zr, Hf) and 1,3-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-imidazolinium chloride [(tBu)(OCO)H-3, 1] cleanly yielded the corresponding M-NHC chloro benzyl derivatives [[(tBu)(OCO)]-M(Cl)(CH2Ph)] (2(Zr) and 2(Hf)) along with 3 equiv of toluene. For both metal complexes, the effective formation of a (k(3)-OCO) metal chelate and the coordination of a benzyl ligand onto the M(IV) metal center were established by NMR and elemental analysis. In contrast, under identical conditions, the reaction of Ti(CH2Ph)(4) with the imidazolinium proligand 1 yielded the unexpected rearranged dimer product 3(Ti), arising from the migration of the Ti-Bn group from the metal center to the C-carbene atom. The molecular structure of 3(Ti) was established by analogy with the X-ray-determined Zr analogue 3(Zr) Compound 3(Zr) quantitatively formed upon heating a benzene solution of 2(Zr), at 60 degrees C. In the solid state, compound 3(Zr), consists of two seven-coordinate mononuclear Zr fragments that are associated by two bridging mu(2)-chloride atoms, confirming the migration of the Zr-Bn moiety from the metal center to the C-carbene atom. Carrying out the reaction of [M(CH2Ph)(4)] (M = Ti, Zr, Hf with imidazolinium proligand 1 in THF led to the quantitative formation of the corresponding rearranged monomeric THF adduct [[(tBu)(OC(Bn)O)]M(Cl)(THF)] (4(Ti)-THF, 4(Zr)-THF, and 4(Hf)-THF), as established by X-ray crystallographic studies in the case of 4(Ti)-THF. Such a THF-promoted benzyl migration was also observed with the dibenzyl Zr and Hf complexes [[(tBu)(OCO)]M(CH2Ph)(2)] (5(Zr), and 5(Hf)), leading to the formation of the corresponding THF-rearranged products [[(tBu)(OC(Bn)O)]M(CH2Ph)(THF)] (6(Zr)-THF and 6(Hf)-THF). The addition of 1 equiv of methylmagnesium bromide (CH3MgBr) or phenylmagnesium bromide (PhMgBr) to 1 equiv of the zirconium dichloro NHC complex [[(tBu)(OCO)]Zr-(Cl-2(THF)] (8) in THF yielded the rearranged products [[(tBu)(OC(Me)O)]M(Cl)THF)] (9(Me)) and [[(tBu)(OC(Ph)O)]M-(Cl)(THF)] (9(Ph)), respectively, as deduced from NMR data. Kinetic studies were carried out on the THF-promoted rearrangement reaction of the benzyl chloro Hf derivative 2Hf in the presence of THF to produce 4(Hf)-THF. These data are consistent with the reaction rate law being first order both in THF and in the THF adduct 2(Hf)-THF. DFT calculations on the Ti, Zr, and Hf systems support a benzyl migration reaction occurring at a transient heptacoordinated bis-THF adduct species of the type [[(tBu)(OCO)]M(Cl)(Bn)(THF)(2)], which may readily form upon THF coordination to 2(Hf)-THF.

  DOI：

  10.1021/om501143t
• 作为产物：
  描述：

  N,N′-bis(2-hydroxy-3,5-di-tert-butylphenyl)ethylenediamine 在 盐酸 作用下， 以 甲醇 、 水 、 甲苯 为溶剂， 反应 24.0h， 生成 (κ3-O,C,O-{(3,5-t-Bu2-C6H2O)2N2C3H4})HfCl(CH2Ph)
  参考文献：
  名称：

  [EN] N-HETEROCYCLIC CARBENE BASED ZIRCONIUM COMPLEXES FOR USE IN LACTONES RING OPENING POLYMERIZATION
  [FR] COMPLEXES DE ZIRCONIUM À BASE DE CARBÈNE N-HÉTÉROCYCLIQUE, À UTILISER DANS LA POLYMÉRISATION DE LACTONE PAR OUVERTURE DE CYCLE

  摘要：

  这项发明报告了基于新型N-杂环卡宾的锆（或铪）络合物，并将其用作内酯环开环聚合的催化剂。这些新型催化剂具有稳健和多功能性，可以控制聚合物的分子量和/或立体化学，并表现出高反应性（适用于低温应用）。特别是，新型催化剂既显示出增强的活性，同时又比先前文献中使用的催化剂具有更好的选择性。

  公开号：

  WO2012076140A1

文献信息

• Neutral and Cationic N-Heterocyclic Carbene Zirconium and Hafnium Benzyl Complexes: Highly Regioselective Oligomerization of 1-Hexene with a Preference for Trimer Formation
  作者：Samuel Dagorne、Stéphane Bellemin-Laponnaz、Charles Romain

  DOI：10.1021/om400182d

  日期：2013.5.13

  Various zirconium and hafnium amido, chloro, and benzyl complexes supported by a tridentate N-heterocyclic carbene bis-phenolate dianionic ligand ((OCO)2–) have been synthesized and structurally characterized. The alcohol elimination reaction of the protio ligand N,N′-bis(2-hydroxy-3,5-di-tert-butylphenyl)-4,5-dihydroimidazolium chloride (1) and the metal alkoxide precursors M(OiPr)4(HOiPr) (M = Zr

  由三齿N-杂环卡宾双酚盐双阴离子配体（（OCO）2–）支撑的各种锆和ha酰胺基，氯和苄基络合物已被合成并进行了结构表征。蛋白质配体N，N'-双（2-羟基-3,5-二叔丁基苯基）-4,5-二氢咪唑氯化物（1）和金属醇盐前体M（O i Pr）的醇消除反应4（HO i Pr）（M = Zr，Hf）和随后的醇盐/氯化物交换反应（添加三甲基甲硅烷基氯，TMSCl）得到相应的Zr和Hf卡宾二氯配合物，为THF加成物：（OCO）MCl 2（THF ）（2a-THF，M ＝ Zr； m ＝ 2。2b-THF，M ＝ Hf）。如通过单晶X射线晶体学研究所确定的，Hf衍生物2b-THF的分子结构证实了所提出的制剂和（OCO）Hf螯合物的有效形成。在Zr的情况下，携带时，原配体1和Zr（NMe 2）4之间的胺消除反应产生相应的Zr酰胺THF加合物（OCO）Zr（NMe 2）（Cl）（THF）（3a-THF）以THF为溶剂，使用CH