NdCl3(THF)3 | 126184-13-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: NdCl3(THF)3
• 英文别名: Neodymium Trichloride Tris(Tetrahydrofuran)；neodymium(3+);oxolane;trichloride
• CAS: 126184-13-2
• 化学式: C₁₂H₂₄Cl₃NdO₃
• 分子量: 466.92
• InChiKey: JVJFMUBKOQAXOQ-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  4.46
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  NdCl3(THF)3 、 [o-C6H4-Ph2P=N-i-Pr]Li*Et2O 以 四氢呋喃 为溶剂， 生成 [o-C6H4-Ph2P=N-i-Pr]2NdCl
  参考文献：
  名称：

  Synthesis and Characterization of Bidentate Rare-Earth Iminophosphorane o-Aryl Complexes and Their Behavior As Catalysts for the Polymerization of 1,3-Butadiene

  摘要：

  O-Aryllithium complexes are easily prepared from stable aminophosphonium salts, and their coordination to rare-earth metals was studied. The ligand to metal ratio in the formed complexes was shown to depend exclusively on the substituent on the nitrogen atom of the ligand. Aryl lithium derivatives 3a and 3b, exhibiting bulky groups (SiMe3 and Bu-t, respectively), gave monocoordinated yttrium complexes 4a-Y and 4b-Y. On the other hand, with aryllithium 3a, possessing an isopropyl at nitrogen, complexes of Y-III, Nd-III and Gd-III with a 2:1 ligand to metal ratio could be obtained. Finally with less hindered ligands such as 6c, featuring an n-butyl substituent, triscoordinated Y, Nd, and La complexes were accessible. X-ray crystal structures have been obtained with all three stoichiometries. These complexes were employed as catalyst precursors for 1,3-butadiene polymerization using various activators. Yttrium complexes were found ineffective, but some neodymium complexes achieved highly selective polymerization of 1,3-butadiene, giving up to 95% of 1,4-cis-polybutadiene albeit with mild activity.

  DOI：

  10.1021/om300389v
• 作为产物：
  描述：

  三氯化钕 在 C₄H₈O 作用下， 以 四氢呋喃 为溶剂， 以90%的产率得到NdCl3(THF)3
  参考文献：
  名称：

  Visseaux, M.; Dormond, A.; Baudry, D., Bulletin de la Societe Chimique de France, 1993, vol. 130, # 2, p. 173 - 184

  摘要：

  DOI：

文献信息

• 一种双席夫碱类稀土配合物及其制备方法和 应用
  申请人：中国石油化工股份有限公司

  公开号：CN107955025B

  公开（公告）日：2019-12-20

  本发明涉及有机合成领域，公开了一种双席夫碱类稀土配合物及其制备方法和应用，该配合物具有式(1)所示的结构：其中，R1为选自由H、甲基、乙基、正丙基、异丙基、伯丁基、仲丁基、叔丁基、甲氧基、乙氧基、正丙氧基、异丙氧基、伯丁氧基、仲丁氧基和叔丁氧基组成的组中的至少一种的基团；R2为选自由H、甲基、乙基、正丙基、异丙基和卤素组成的组中的至少一种基团。本发明提供的双席夫碱类稀土配合物具有催化极性单体聚合的功能，由双席夫碱类稀土配合物催化极性单体聚合时的转化率高，且聚合物的分子量大。
• Syntheses, characterization and crystal structures of 5,14-dihydro-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine rare earth(III) complexes
  作者：Zenglin Wang、Ninghai Hu、Kazunori Sakata、Mamoru Hashimoto

  DOI：10.1039/a900100j

  日期：——

  Rare earth(III) complexes of tmtaa, Ln(tmtaa)(Htmtaa)·0.6CH2Cl2 (Ln = Pr 1, Nd 2, Sm 3, Gd 4, Tb 5, Er 6 and Yb 7; H2tmtaa = 5,14-dihydro-6,8,15,17-tetramethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine) were prepared by reaction of Li2tmtaa with LnCl3(THF)3 in tetrahydrofuran (THF). The complexes were characterized by infrared, mass and electronic spectra as well as DSC measurement. The crystal structures of Ln(tmtaa)(Htmtaa)·0.6CH2Cl2 (Ln = Sm 3, Tb 5, Er 6 and Yb 7) were determined by X-ray crystal diffraction. The complexes are isomorphous and the crystals belong to a monoclinic crystal system with the space group of C2/m. The rare earth(III) ions in the complexes are coordinated by eight nitrogen atoms from tmtaa and Htmtaa to form eight-coordinate sandwich complexes. The average Ln–N bond lengths for tmtaa and Htmtaa are 2.463(7) and 2.543(7) Å for 3, 2.438(7) and 2.540(7) Å for 5, 2.406(9) and 2.474(9) Å for 6 and 2.388(8) and 2.495(8) Å for 7, respectively. The tmtaa and Htmtaa in the complexes adopt markedly saddle conformations and coordinate to the rare earth(III) ions as delocalized conjugated π-electron systems. The acidic hydrogen in the complexes does not bind strongly to any of the nitrogen atoms of tmtaa or Htmtaa, but may belong to the four nitrogen atoms of Htmtaa. The influences of sandwich structures on the dihedral angles of the ligands were studied.

  稀土(III)络合物 Ln(tmtaa)(Htmtaa)-0。6CH2Cl2（Ln = Pr 1、Nd 2、Sm 3、Gd 4、Tb 5、Er 6 和 Yb 7；H2tmtaa = 5,14-二氢-6,8,15,17-四甲基二苯并[b,i][1,4,8,11]四氮杂环十四烷）是由 Li2tmtaa 与 LnCl3(THF)3 在四氢呋喃（THF）中反应制备的。通过红外光谱、质谱、电子能谱和 DSC 测量对这些复合物进行了表征。通过 X 射线晶体衍射确定了 Ln(tmtaa)(Htmtaa)-0.6CH2Cl2（Ln = Sm 3、Tb 5、Er 6 和 Yb 7）的晶体结构。这些配合物是同构的，晶体属于单斜晶系，空间群为 C2/m。配合物中的稀土（III）离子与来自 tmtaa 和 Htmtaa 的八个氮原子配位，形成八配位夹心配合物。tmtaa 和 Htmtaa 的 Ln-N 键平均长度分别为：3 为 2.463(7) Å 和 2.543(7) Å，5 为 2.438(7) Å 和 2.540(7) Å，6 为 2.406(9) Å 和 2.474(9) Å，7 为 2.388(8) Å 和 2.495(8) Å。配合物中的 tmtaa 和 Htmtaa 采用明显的鞍状构象，并以脱局域共轭 π 电子系统的形式与稀土（III）离子配位。配合物中的酸性氢与 tmtaa 或 Htmtaa 的任何一个氮原子的结合力都不强，但可能属于 Htmtaa 的四个氮原子。研究了夹层结构对配体二面角的影响。
• Organometallic Early Lanthanide Clusters:  Syntheses and X-ray Structures of New Monocyclopentadienyl Complexes
  作者：Fanny Bonnet、Marc Visseaux、Denise Barbier-Baudry、Abderrafia Hafid、Estelle Vigier、Marek M. Kubicki

  DOI：10.1021/ic035444l

  日期：2004.6.1

  The reaction of Ln(BH(4))(3)(THF)(3) or LnCl(3)(THF)(3) with 1 equiv of KCp*' ligand (Cp' = C(5)Me(4)n-Pr) afforded the new monocyclopentadienyl complexes Cp*'LnX(2)(THF)(n) (X = BH(4), Ln = Sm, n = 1, 1a, Ln = Nd, n = 2, 1b; X = Cl, Ln = Sm, n = 1, 3a) and [Cp*'LnX(2)](n') (X = BH(4), n' = 6, Ln = Sm, 2a, Ln = Nd, 2b; X = Cl, Ln = Nd, 4b). All these compounds were characterized by elemental analysis

  Ln（BH（4））（3）（THF）（3）或LnCl（3）（THF）（3）与1当量的KCp *'配体（Cp'= C（5）Me（4） n-Pr）提供了新的单环戊二烯基络合物Cp *'LnX（2）（THF）（n）（X = BH（4），Ln = Sm，n = 1，1a，Ln = Nd，n = 2，1b; X = Cl，Ln = Sm，n = 1，3a）和[Cp *'LnX（2）]（n'）（X = BH（4），n'= 6，Ln = Sm，2a，Ln = Nd ，2b； X ＝ Cl，Ln ＝ Nd，4b）。所有这些化合物均通过元素分析和（1）H NMR表征。混合氢硼氢化/氯桥联的晶体[Cp *'（6）Ln（6）（BH（4））（12-x））Cl（x）（THF）（n'）]（x = 10，n' ＝ 4，Ln ＝ Sm，2a′，Ln ＝ Nd，2b′； x ＝ 5，n ＝ 2，Ln ＝ Sm，2a′′）也被
• Rare Earth Metal Alkyl Complexes with Methyl-Substituted Triazacyclononane-amide Ligands:  Ligand Variation and Ethylene Polymerization Catalysis
  作者：Sergio Bambirra、Daan van Leusen、Cornelis G. J. Tazelaar、Auke Meetsma、Bart Hessen

  DOI：10.1021/om060870a

  日期：2007.2.1

  Comparative testing in catalytic ethylene polymerization showed that the catalyst activity is most strongly influenced by the metal ionic radius, but that variations in the ligand backbone and substitution pattern do influence other factors, such as polymer molecular weight and catalyst stability. Catalysts with the intermediately sized rare earth metal yttrium generally showed the highest activity, but

  制备了一系列具有通式[Me 2 TACN-（B）-NR] M（CH 2 SiMe 3）2（TACN = 1,4,7-三氮杂环壬烷，B =（CH 2）的稀土金属二烷基配合物2，SiMe 2 ; R = t Bu，sec Bu，n卜; M = Sc，Y，Nd，La）。对于M = Sc，也可以使用混合的单烷基一氯配合物。这些配合物的选定实例在结构上得到了表征，并显示出畸变的八面体环境中的金属。使用路易斯或布朗斯台德酸活化剂，可以将二烷基化合物转化为相应的单烷基阳离子，并通过NMR光谱对其进行表征。催化乙烯聚合的比较测试表明，催化剂活性受金属离子半径的影响最大，但是配体主链和取代方式的变化确实会影响其他因素，例如聚合物分子量和催化剂稳定性。具有中等大小的稀土金属钇的催化剂通常显示出最高的活性，但是其中一些催化剂会产生分子量分布较宽的聚乙烯，表明存在多点行为。从理论上讲，这可能是由于分子间配体加扰过
• One Ligand Fits All:  Cationic Mono(amidinate) Alkyl Catalysts over the Full Size Range of the Group 3 and Lanthanide Metals
  作者：Sergio Bambirra、Marco W. Bouwkamp、Auke Meetsma、Bart Hessen

  DOI：10.1021/ja0475297

  日期：2004.8.1

  Using a sterically demanding amidinate ancillary ligand and an in situ alkylation procedure, neutral mono(amidinate) dialkyl and cationic mono(amidinate) monoalkyl complexes were prepared for metals spanning the full size range of the group 3 and lanthanide metals. The activity of the cationic monoalkyls in catalytic ethene polymerization was found to vary by over 2 orders of magnitude depending on

  使用空间要求高的脒辅助配体和原位烷基化程序，制备了中性单（脒）二烷基和阳离子单（脒）单烷基配合物，用于跨越第 3 族和镧系金属的全尺寸范围的金属。发现在催化乙烯聚合中阳离子单烷基的活性根据金属离子半径变化超过 2 个数量级，发现中间金属尺寸是最有效的。