[NdCl₃(1,2-dimethoxyethane)]

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [NdCl₃(1,2-dimethoxyethane)]
• 英文别名: [NdCl3(dme)]；1,2-Dimethoxyethane;trichloroneodymium；1,2-dimethoxyethane;trichloroneodymium
• 化学式: C₄H₁₀Cl₃NdO₂
• 分子量: 340.721
• InChiKey: OWYDKGVEFPWBNN-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  2.35
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [NdCl₃(1,2-dimethoxyethane)] 在 THF 作用下， 以 四氢呋喃 为溶剂， 以48%的产率得到[NdCl(μ-Cl)2(tetrahydrofuran)2]n
  参考文献：
  名称：

  在温和条件下改进无水镧系氯化物的制备

  摘要：

  摘要在1，12-二甲氧基乙烷存在下，由亚硫酰氯和水在原位生成的氯化氢在温和的条件下将镧系元素（Ln）的氧化物或碳酸盐转化为相应的溶剂化无水氯化物LnCl 3（ether）n。

  DOI：

  10.1016/0020-1693(95)04568-6
• 作为产物：
  描述：

  乙二醇二甲醚 、 neodimium(III) chloride * 2 tetrahydrofuran 以 乙二醇二甲醚 为溶剂， 生成 [NdCl₃(1,2-dimethoxyethane)]
  参考文献：
  名称：

  溶剂化和非溶剂化镧系元素卤化物在Friedel-Crafts酰化反应中的催化活性

  摘要：

  无水镧系元素卤化物（氯化物和溴化物）可以作为Friedel-Crafts酰化反应的均相催化剂。催化活性与这些无水盐的溶解度有关。更具溶解性的THF或二恶烷（Diox。）钕和sa加合物是更具活性的催化剂。

  DOI：

  10.1016/s1381-1169(00)00285-5

文献信息

• <i>N</i> , <i>N</i> ‐Dialkylcarbamato Lanthanide Complexes, a Series of Isotypical Coordination Compounds
  作者：Ulrich Baisch、Daniela Belli Dell’Amico、Fausto Calderazzo、Luca Labella、Fabio Marchetti、Alessandra Merigo

  DOI：10.1002/ejic.200300649

  日期：2004.3

  (Ln = Pr, Nd, Eu, Gd, Ho, Er, Yb, Lu, R = iPr; Ln = Nd, Eu, Gd, R = Bu; Ln = Nd, R = Et), using [LnCl3(ether)x] (ether = THF or dimethoxyethane, DME), NHR2, and CO2 are reported. X-ray diffraction of the diisopropylcarbamato derivatives, including a reinvestigation of [Yb4(O2CNiPr2)12], showed these complexes to be tetranuclear and isotypical over a range of 12 atomic numbers. The lanthanide contraction

  [Ln(O2CNR2)3] (Ln = Pr, Nd, Eu, Gd, Ho, Er, Yb, Lu, R = iPr; Ln = Nd, Eu, Gd ，R = Bu；Ln = Nd，R = Et)，使用 [LnCl3(ether)x]（醚 = THF 或二甲氧基乙烷，DME），报告了 NHR2 和 CO2。二异丙基氨基甲酸衍生物的 X 射线衍射，包括对 [Yb4(O2CNiPr2)12] 的重新研究，表明这些配合物在 12 个原子序数的范围内是四核和同型的。基于四种不同类型的 Ln-O 键的长度评估了镧系元素收缩。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• Re-investigation of ortho-metalated N,N-dialkylbenzylamine complexes of rare-earth metals. First structurally characterized arylates of neodymium and gadolinium Li[LnAr4]
  作者：Alex R. Petrov、Konstantin A. Rufanov、Klaus Harms、Jörg Sundermeyer

  DOI：10.1016/j.jorganchem.2008.12.020

  日期：2009.4

  solv = THF, DME; n = 1–3 in reactions with ortho-lithiated dimethyl-benzylamine Li(dmba) has been studied. An improved protocol towards homoleptic tris-aryl complexes of the type [Ln(dmba)3], Ln = Y, Er and Yb has been developed and molecular structures of these complexes have been established by X-ray crystallography. For the first time stable homoleptic lithium ate-complexes of the type Li[Ln(dmba)4]

  醚配体在[LnCl 3（solv）n ]中的影响，solv = THF，DME； 与邻位锂化的二甲基苄基胺Li（dmba）的反应中，n = 1-3 。已经开发了针对[Ln（dmba）3 ]，Ln = Y，Er和Yb类型的均化三芳基配合物的改进方案，并通过X射线晶体学确定了这些配合物的分子结构。首次分离出Li [Ln（dmba）4 ]类型（Ln = Gd，Nd）的稳定的均相锂盐复合物，并对其结构进行了表征。它们合成的成功很大程度上取决于适当的[LnCl 3（solv）n]前体，例如[GdCl 3（dme）2 ]，[NdCl 3（dme）]和无THF反应条件。讨论了影响具有dmba型配体的镧系元素三芳基配合物可能降解途径的因素。
• Tetrahydropentalenyl-phosphazene constrained geometry complexes of rare-earth metal alkyls
  作者：Noa K. Hangaly、Alexander R. Petrov、Michael Elfferding、Klaus Harms、Jörg Sundermeyer

  DOI：10.1039/c3dt53596g

  日期：——

  [Lu(CH2SiMe3)3(thf)2] or with rare-earth metal halides and three equivalents of LiCH2SiMe3 produced the desired bis(alkyl) Cp™PN complexes: [Cp™PN}M(CH2SiMe3)2] (M = Sc (1Ad, 1Dip), Lu (2Ad, 2Dip), Y (3Ad, 3Dip), Sm (4Ad), Nd (5Ad), Pr (6Ad), Yb (7Ad)). These complexes were characterized by extensive NMR studies for the diamagnetic and the paramagnetic complexes with full signal assignment. An almost

  Cp™HPPh 2（1，二苯基（4,4,6,6-四甲基-1,4,5,6-四氢戊二烯-2-基）膦）与有机叠氮化物AdN 3和DipN 3（Ad = 1 -金刚烷基； Dip = 2,6-二异丙基苯基）导致形成两个新的CpPN配体：P-氨基-环戊二烯叉叉基-正膦（Cp™PPh 2 NHAd；L Ad H）和P-环戊二烯基-亚氨基正膦（ Cp™HPPh 2 NDip; L浸入H）。两者均通过NMR光谱和X射线结构分析来表征。对于这两种化合物，仅观察到一种异构体。两者都不具有任何可检测到的质子或元亲异构体。这些配体与[Lu（CH 2 SiMe 3）3（thf）2 ]或与稀土金属卤化物和三当量的LiCH 2 SiMe 3的反应产生了所需的双（烷基）Cp™PN络合物：[Cp™ PN} M（CH 2 SiMe 3）2 ]（M = Sc（1 Ad，1 Dip），Lu（2 Ad，2 Dip），Y（3Ad，3
• Metal complex compositions and their use as catalysts to produce polydienes
  申请人：Thiele K-H Sven

  公开号：US20050090383A1

  公开（公告）日：2005-04-28

  This invention relates to metal complex compositions, their preparation and their use as catalysts to produce polymers of conjugate dienes through polymerization of conjugated diene monomers. The used metal complex compositions are transition metal compounds in combination with an activator compound, optionally with a transition metal halide compound and optionally a catalyst modifier and optionally an inorganic or organic support material. The metal complexes comprises metals of group 3 to 10 of the Periodic System of the Elements in combination with activators, and optionally transition metal halide compounds of groups 3 to 10 of the Periodic Table of the Elements including lanthanide metals and actinide metals and optionally, catalyst modifiers, especially Lewis acids and optionally an inorganic or organic support material. More in particular the invention relates metal complex compositions, their preparation and their use as catalysts to produce homopolymers of conjugated dienes, preferably, but not limited to, through polymerization of 1,3-butadiene or isoprene.

  本发明涉及金属配合物组合物、它们的制备以及它们作为催化剂的用途，通过共轭二烯单体的聚合来产生共轭二烯聚合物。所使用的金属配合物组合物是转移金属化合物与活化剂化合物的组合，可选地与转移金属卤化物化合物和可选的催化剂改性剂以及无机或有机支撑材料组合使用。金属配合物包括元素周期表中3到10组的金属与活化剂组合，可选地包括元素周期表中3到10组的金属卤化物，包括镧系金属和锕系金属，可选地包括催化剂改性剂，特别是路易斯酸，以及可选的无机或有机支撑材料。更具体地，本发明涉及金属配合物组合物、它们的制备以及它们作为催化剂的用途，用于生产共轭二烯的同聚物，优选但不限于通过1,3-丁二烯或异戊二烯的聚合。
• Cyclopentadienylphosphazene (CpPN) Complexes of Rare-Earth Metals: Synthesis, Structural Characterization, and Hydroamination Catalysis
  作者：Noa K. Hangaly、Alex R. Petrov、Konstantin A. Rufanov、Klaus Harms、Michael Elfferding、Jörg Sundermeyer

  DOI：10.1021/om200264n

  日期：2011.9.12

  Synthesis of the first series of rare-earth-metal constrained geometry complexes containing the P-(1-adamantylamino)-P-dimethyl-tetramethyl-cyclopentadienylidene-phosphorane ligand C(5)Me(4)PMe(2)NHAd, (CpPN)-P-#}H, was accomplished. This monoanionic chelate ligand is isoelectronically related to the classical dianionic cyclopentadienyl-silylamine ligand C5Me4HSiMe2-NHtBu, (CpSiN)-Si-#}H-2. The ligand stabilizes dialkyls [(CpPN)-P-#}M(CH2SiMe3)(2)] (M = Sc, 1; Lib 2; Y, 3; Sm, 4; Nd, 5; Pr, 6; Ce, 7) over the full range of group 3 and lanthanide cation radii. Results of NMR studies of these crystalline alkyls, XRD molecular structures, and a preliminary study revealing the high catalytic activity of complexes 3-6 in the intramolecular hydroamination/cyclization are reported. The catalytic experiments reveal a trend in activity Lu < Y < Sm < Nd <= Pr resembling the trend in rare-earth-metal radii. Interestingly they reveal a distinctive substrate-dependent first-order kinetic profile for all metals investigated. The reaction of the precatalyst 3 with 1.6 equiv of the standard substrate 2,2-dimethylpenten-4-ylamine leads to a fast and selective formation of substrate complex [(CpPN)-P-#}Y(NHCH2CMe2CH2CH-=CH2)(2)] (8). Fast cyclization was observed only after addition of more than 2 equiv of amine substrate. A noninsertive mechanism involving a six-membered transition state by a concerted C-N bond formation and N-H bond cleavage at a 3:1 substrate to complex ratio is suggested on the basis of these findings.