Zr(NEt2)4 | 943987-58-4

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: Zr(NEt2)4
• 英文别名: diethylazanide;zirconium(4+)
• CAS: 943987-58-4
• 化学式: C₁₆H₄₀N₄Zr
• 分子量: 379.744
• InChiKey: GOVWJRDDHRBJRW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Zr(NEt2)4 以 正戊烷 为溶剂， 生成 [C4H2N(2,5-CH2NMe2)2Zr(pyrrole(-H))3]
  参考文献：
  名称：

  Zirconium and hafnium amide, alkoxide, and pyrrolyl complexes manifesting with pyrrolyl-linked N-donor ligands: Syntheses, characterization, and ring opening polymerization of ε-caprolactone

  摘要：

  A series of zirconium and hafnium alkoxide and amide complexes containing symmetrical tridentate pyrrolyl ligand, [C4H2NH(2,5-CH2NMe2)(2)] have been synthesized conveniently by treatment of 2,6-di-tert-butylphenol, tert-butanol or pyrrole in pentane and their reactivity over ring opening polymerization of epsilon-caprolactone have been carried out. Reactions of [C4H2NH(2,5-CH2NMe2)(2)] with M(NEt2)(4) (M = Zr or Hf) originate [C4H2N(2,5-CH2NMe2)(2)]M(NEt2)(3) (1, M = Zr; 2, M = Hf). Furthermore, reactions of [C4H2N(2,5-CH2NMe2)(2)]M(NEt2)(3) with 2,6-di-tert-butylphenol, tert-butanol or pyrrole afford [C4H2N(2,5-CH2NMe2)(2)]M(OC6H3-2,6-Bu-t(2))(NEt2)(2) (3, M = Zr; 4, M = Hf), [C4H2N(2,5-CH2NMe2)(2)]M((OBu)-Bu-t)(3) (5, M = Zr; 6, M = Hf) and [C4H2N(2,5-CH2NMe2)(2)]M(C4H4N)(3) (7, M = Zr; 8, M = Hf), respectively, in satisfactory yield. All the complexes have been characterized by NMR spectra as well 3, 4 and 6 subjected to the X-ray diffraction analysis. Complexes 3-8 have been used as initiators for the ring-opening polymerization of epsilon-caprolactone and observed broad PDI values (1.84-2.75) representing multiple reactivity centers of these complexes. (C) 2011 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2011.09.001
• 作为产物：
  描述：

  二乙胺 生成 Zr(NEt2)4
  参考文献：
  名称：

  DIRK, STEINBORN;INES, WAGNER;RUBOIF, TAUBE

  摘要：

  DOI：

文献信息

• Amidate complexes of titanium and zirconium: a new class of tunable precatalysts for the hydroamination of alkynesElectronic supplementary information (ESI) available: experimental details. See http://www.rsc.org/suppdata/cc/b3/b304176j/
  作者：Chunyu Li、Robert K. Thomson、Bronwyn Gillon、Brian O. Patrick、Laurel L. Schafer

  DOI：10.1039/b304176j

  日期：——

  A series of bis(amidate)group 4-bis(amido) complexes have been prepared, characterized and have been shown to be highly tunable precatalysts for both the intra- and intermolecular hydroamination of alkynes.

  一系列含双（亚胺酸盐）的第4族双（酰胺）配合物已经被制备、表征，并显示出是高度可调的前催化剂，适用于炔烃的分子内和分子间氢胺化反应。
• Non-planar co-ordination of C2-symmetric biaryl-bridged Schiff-base ligands: well expressed chiral ligand environments for zirconium †
  作者：Paul R. Woodman、Ian J. Munslow、Peter B. Hitchcock、Peter Scott

  DOI：10.1039/a906788d

  日期：——

  The C2-symmetric Schiff-base proligand (H2L1) synthesized by condensation of 2,2′-diamino-6,6′-dimethylbiphenyl and 3,5-di-tert-butylsalicylaldehyde reacted in its deprotonated form with [MCl4(THF)2] (M = Zr or Hf) to give [ML1Cl2]. The molecular structures of these complexes show that they belong to the hitherto unknown cis-cis class of quadridentate Schiff-base complex. Most importantly, the two chloride ligands occupy mutually cis co-ordination sites in a well expressed chiral ligand environment that is structurally analogous to that of the ansa-metallocenes. Alkylations of the zirconium complex were unsuccessful, but an unstable complex [ZrL1(CH2Ph)2] was synthesized from H2L1 and Zr(CH2Ph)4. Amido complexes [ZrL1(NR2)2] (R = Me or Et; R2 = HBut) were synthesized by substitution reactions of [ZrL1Cl2] and by reaction of H2L1 with Zr(NR2)4. The reactions of [ZrL1(NR2)2] (R = Me or Et) with SiH(OEt)3 and SiMe3Cl gave [ZrL1(OEt)2] and [ZrL1Cl2] respectively. The reaction of [ZrL1Cl2] with LiOPh gave [ZrL1(OPh)2]. The molecular structure of the latter confirms that it also has the cis-cis structure and also indicates the presence of edge–face arene interactions between the phenoxide ligands and the salicylidene units. The reaction of [ZrL1Cl2] with LiAlH4 in pyridine (py) led to reduction in situ of the imine groups and elimination of both chloride ligands to give a complex containing the quadruply deprotonated reduced form of L1, i.e. [ZrL2(py)2]. This complex is also formed by reaction of H4L2 with Zr(NR2)4 in pyridine.

  通过2,2'-二氨基-6,6'-二甲基联苯和3,5-二叔丁基水杨醛的缩合反应合成的C2对称席夫碱前体（H2L1），在其去质子化形式下与[MCl4(THF)2]（M = Zr或Hf）反应，得到[ML1Cl2]。这些配合物的分子结构显示，它们属于迄今未知的cis-cis型四齿席夫碱配合物。最重要的是，两个氯配体在结构上类似于ansa-金属有机物的手性配体环境中占据相互cis配位位点。锆配合物的烷基化未能成功，但通过H2L1与Zr(CH2Ph)4合成了一种不稳定的配合物[ZrL1(CH2Ph)2]。通过[ZrL1Cl2]的取代反应和H2L1与Zr(NR2)4的反应，合成了氨基配合物[ZrL1(NR2)2]（R = Me或Et；R2 = HBut）。[ZrL1(NR2)2]（R = Me或Et）与SiH(OEt)3和SiMe3Cl的反应分别得到了[ZrL1(OEt)2]和[ZrL1Cl2]。[ZrL1Cl2]与LiOPh的反应得到了[ZrL1(OPh)2]。后者的分子结构确认其也具有cis-cis结构，并且表明苯氧基配体与水杨醛单元之间存在边缘-面芳烃相互作用。[ZrL1Cl2]在吡啶（py）中与LiAlH4反应，导致亚胺基团的还原和两个氯配体的消除，得到含有四重去质子化还原形式L1的配合物，即[ZrL2(py)2]。该配合物也可以通过H4L2与Zr(NR2)4在吡啶中的反应形成。
• A Synthetic Route to a Molecular Galloxane Dihydroxide and Its Group 4 Heterobimetallic Compounds
  作者：Erandi Bernabé-Pablo、Vojtech Jancik、Mónica Moya-Cabrera

  DOI：10.1021/ic4010054

  日期：2013.6.17

  a N-heterocyclic carbene, as a HCl acceptor, led to the unprecedented molecular galloxane dihydroxide [MeLGa(OH)}2(μ-O)] (2) in high yield. Compound 2 was used in the assembly of the heterobimetallic galloxanes with group 4 metals [(MeLGa)2(μ-O)}(μ-O)2M(NR2)2}] (M = Ti, R = Me (6); M = Zr (7), Hf (8), R = Et).

  的受控水解我LGaCl 2（我L = HC [（CME）N（2,4,6-ME 3 c ^ 6 ħ 2）] 2 - （）1在存在下）ñ -杂环卡宾，作为盐酸受体，以高收率产生了前所未有的分子氢氧烷二氧六环[ Me LGa（OH）} 2（μ-O）]（2）。化合物2用于杂双金属镓氧烷与第4组金属[（Me LGa）2（μ-O）}（μ-O）2 M（NR 2）2}]（M = Ti，R = Me（6）； M = Zr（7），Hf（8），R = Et）。
• Structure, Bonding, and Reactivity of Ti and Zr Amidate Complexes:  DFT and X-Ray Crystallographic Studies
  作者：Robert K. Thomson、Federico E. Zahariev、Zhe Zhang、Brian O. Patrick、Yan Alexander Wang、Laurel L. Schafer

  DOI：10.1021/ic0502980

  日期：2005.11.1

  synthesis. In solution, these complexes are observed to isomerize on the NMR time scale, with one isomer being predominant. Bonding in the bis(amidate)-bis(amido) complexes was investigated by DFT calculations. The geometric isomers predicted by theory matched the experimentally observed results, within experimental error. The orbitals associated with amidate-metal bonding are energetically well below

  易于制备且高度模块化的有机酰胺配体已用于通过质子分解合成一系列新的双（酰胺酸酯）-双（酰胺基）Ti和Zr配合物。这些配合物已经通过NMR光谱和X射线晶体学进行了结构表征。这些配合物的固态分子结构表明，酰胺化物配体以独有的双齿方式与金属中心结合，形成离散的单体种类。这些物质中的几何异构现象高度依赖于合成中所用配体的空间特征。在溶液中，观察到这些络合物在NMR时间尺度上异构化，其中以一种异构体为主。通过DFT计算研究了双（酰胺基）-双（酰胺基）配合物中的键合。理论预测的几何异构体在实验误差范围内与实验观察到的结果相符。与酰胺化物-金属键相关的轨道在能量上远低于边界轨道。这些络合物中的HOMO是与酰胺配体与金属键合特征相关的pi轨道，而LUMO在所有情况下都是金属中心上的空d轨道。
• Enantiospecific synthesis of a planar chiral bidentate indenyl–alkoxide complex of zirconium using an axially chiral indene ligand
  作者：Robert W. Baker、Brian J. Wallace

  DOI：10.1039/a903740c

  日期：——

  The reaction of axially chiral (M)-1-(2′-methyl-3′-indenyl)- naphthalene-2-methanol 3 with Zr(NEt2)4 enantiospecifically provides the planar chiral complex (P)-bis(diethylamido)-[1-(2′-methyl-1′-indenyl)naphthalene-2-methoxo]- zirconium 7.

  轴向手性化合物 (M)-1-(2′-甲基-3′-茚基)-萘-2-醇 3 与 Zr(NEt2)4 发生反应，选择性地生成平面手性复合物 (P)-双(二乙胺基)-[1-(2′-甲基-1′-茚基)萘-2-甲氧基]-锆 7。