neodymium(III)tris(1,3-bis-(trimethylsilyl)cyclopentadienyl) | 170379-31-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: neodymium(III)tris(1,3-bis-(trimethylsilyl)cyclopentadienyl)
• 英文别名: (1,3-bis-(trimethylsilyl)cyclopentadienyl)₃Nd(III)；Nd(C₅H₃(SiMe₃)₂)₃；Nd(Cp'')₃；[Nd(η-C5H3(SiMe3)2-1,3)3]；((Me3Si)2C5H3)3Nd；neodymium(3+);trimethyl-(3-trimethylsilylcyclopenta-1,4-dien-1-yl)silane
• CAS: 170379-31-4
• 化学式: C₃₃H₆₃NdSi₆
• 分子量: 772.616
• InChiKey: MKZHJNKIUSBUSE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  neodymium(III)tris(1,3-bis-(trimethylsilyl)cyclopentadienyl) 、 trimethylamine hydrofluoric acid 以 四氢呋喃 为溶剂， 以89%的产率得到[((Me3Si)2C5H3)2NdF]2
  参考文献：
  名称：

  Synthesis, Molecular Structure, and Reactivity of Organolanthanide Fluoride Complexes, [{(Me₃Si)₂C₅H₃}₂Ln(μ-F)]₂ (Ln = La, Nd, Sm, Gd) and [(C₅H₅)₂Ln(μ-F)(THF)]₂ (Ln = Y, Yb)

  摘要：

  Treatment of Me3NHF with I equiv of [(Me3Si)(2)C5H3](3)Ln or (C5H5)(3)Ln in THF gave [{-(Me3Si)(2)C5H3}(2)LnF](2) (Ln = La (1), Nd (2), Sm (3), Gd (4)) or [(C5H5)(2)LnF(THF)](2) (Ln = Y (5), Yb (6)) in moderate to good yield. All of them were fully characterized by elemental analyses, spectroscopy, and X-ray analyses. Compound 3 reacted with Na, AlCl3, (C6H5)(3)-SiOH, and 2,6-(Pr2C6H3OH)-C-i to form [(Me3Si)(2)C5H3](2)Sm(THF), [{(Me3Si)(2)C5H3}(2)SmCl](2), [(C6H5)(3)SiO](3)Sm(THF)(3) (7), and [2,6-(Pr2C6H3O)-C-i](3)Sm(THF)(3) (8), respectively. The molecular structures of [{(Me3Si)(2)C5H3}(2)SmCl](2), 7, and 8 were confirmed by X-ray diffraction study. The 3/NaH system can convert C6H5Br into C6H6 in 32% yield.

  DOI：

  10.1021/om980162s
• 作为产物：
  描述：

  三氯化钕 、 1,3-ditrimethylsilylcyclopentadienyl potassium 以 四氢呋喃 为溶剂， 以95%的产率得到neodymium(III)tris(1,3-bis-(trimethylsilyl)cyclopentadienyl)
  参考文献：
  名称：

  Activation of a CO bond by reaction of a tris(cyclopentadienyl)lanthanide complex with an alkali metal in dimethoxyethane (DME); crystal structures of [Ndη-C5H3(SiMe3)2-1,32(μ-OMe)2Li(DME)] and [{Ce(η-C5H3tBu2-1,3)2(μ-OMe)2]

  摘要：

  The reaction of [LnCp''(3)] [Ln = Ce, Cp'' = eta-C(5)H(3)(t)Bu(2)-1,3 or eta-C5H3(SiMe(3))(2)-1,3; or Ln = Nd and Cp'' = eta-C5H3(SiMe(3))(2)-1,3] with metallic lithium or potassium in dimethoxyethane (DME) at ambient temperature gave in high yield [{LnCp''(2)(mu-OMe)}(2)] [Ln = Ce and Cp'' = eta-C5H3(SiMe(3))(2)-1,3 (1) or eta-C(5)H(3)(t)Bu(2)-1,3 (2); or Ln = Nd and Cp'' = eta-C5H3(SiMe(3))(2)-1,3 (3)] or [NdCp''(2)(mu-OMe)(2)Li(DME)] (Cp'' = eta-C5H3(SiMe(3))(2)-1,3) (4). The crystal structures of complexes 2 and 4 are reported. Complex 4 is the first structurally characterized heterobimetallic lanthanocene-alkoxo-lithium.

  DOI：

  10.1016/0022-328x(95)00330-s

文献信息

• Small-Scale Metal-Based Syntheses of Lanthanide Iodide, Amide, and Cyclopentadienyl Complexes as Analogues for Transuranic Reactions
  作者：Cory J. Windorff、Megan T. Dumas、Joseph W. Ziller、Andrew J. Gaunt、Stosh A. Kozimor、William J. Evans

  DOI：10.1021/acs.inorgchem.7b01968

  日期：2017.10.2

  synthesized by dissolving 1-Ln in THF. The viability of these small-scale samples as starting materials for amide and cyclopentadienyl f-element complexes was tested by reacting KN(SiMe3)2, KCp′ (Cp′ = C5H4SiMe3), KCp′′ (Cp′′ = C5H3(SiMe3)2-1,3), and KC5Me4H with 1-Ln generated in situ. These reactions produced Ln[N(SiMe3)2]3 (4-Ln), Cp′3Ln (5-Ln), Cp″3Ln (6-Ln), and (C5Me4H)3Ln (7-Ln), respectively. Small-scale

  为了优化从金属开始的放射性p的毫克级反应，已经研究了Pu类似物La，Ce和Nd的小规模反应。已经研究了这些镧系金属在醚和吡啶中用碘氧化的方法，LnI 3（Et 2 O）x（1-Ln；x = 0.75-1.9）和LnI 3（py）4（2-Ln； py =吡啶，NC 5 H 5）的合成规模为15毫克至2克。通过溶解1-Ln合成THF加合物LnI 3（THF）4（3-Ln）在THF中。通过使KN（SiMe 3）2，KCP'（CP'= C 5 H 4 SiMe 3），KCP''（CP' ′= C 5 H 3（SiMe 3）2 -1,3）和带有1-Ln的KC 5 Me 4 H原位生成。这些反应产生的LN [N（森达3）2 ] 3（4-LN）中，CP' 3 LN（5-LN）中，CP“ 3 LN（6-LN）和（C 5 Me 4 H）3 Ln（7-Ln）。CP'的小规模的样品3的Ce（5-铈）和CP' 3的Nd（5
• The roles of 4f- and 5f-orbitals in bonding: a magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study
  作者：W. W. Lukens、M. Speldrich、P. Yang、T. J. Duignan、J. Autschbach、P. Kögerler

  DOI：10.1039/c6dt00634e

  日期：——

  generally significantly more difficult for actinide complexes than for lanthanide complexes. In this study, a set of analogous neodymium(III) and uranium(III) tris-cyclopentadienyl complexes and their isocyanide adducts was characterized by electron paramagnetic resonance (EPR) spectroscopy and magnetic susceptibility. The crystal field model was parameterized by combined fitting of EPR and susceptibility

  探讨了 4f3/5f3 Cp′′3M 和 Cp′′3M·烷基异氰化物络合物的电子结构，其中 Cp′′ 是 1,3-双-（三甲基甲硅烷基）环戊二烯基，重点是 f 轨道的分裂，这提供了有关金属-配体相互作用强度的信息。虽然已经详细报道了许多镧系元素配合物中的 f 轨道分裂，但在卤化物和氧化物化合物以外的系统中，锕系元素配合物中 f 轨道分裂的实验测定仍然很少见，因为实验方法，即晶场分析，通常对锕系元素配合物比镧系元素配合物要困难得多。在本研究中，通过电子顺磁共振 （EPR） 波谱和磁化率对一组类似的钕 （III） 和铀 （III） 三环戊二烯基配合物及其异氰化物加合物进行了表征。通过结合 EPR 和磁化率数据拟合，对晶体场模型进行参数化，从而准确描述 f 轨道分裂。还使用密度泛函理论研究了异氰化物衍生物，从而产生了与晶体场拟合一致的 f 轨道分裂，并通过多参考波函数计算支持从晶体场计算得出的电子结构分析。结果强调
• Trimethylsilyl versus Bis(trimethylsilyl) Substitution in Tris(cyclopentadienyl) Complexes of La, Ce, and Pr: Comparison of Structure, Magnetic Properties, and Reactivity
  作者：Chad T. Palumbo、Lucy E. Darago、Cory J. Windorff、Joseph W. Ziller、William J. Evans

  DOI：10.1021/acs.organomet.7b00881

  日期：2018.3.26

  of cyclopentadienyl ligand substitution in complexes of new +2 ions of the lanthanides, comparisons in reactivity and spectroscopic and magnetic properties have been made between [K(crypt)][Cp′3Ln], 1-Ln (Cp′ = C5H4SiMe3; crypt = 2.2.2-cryptand; Ln = La, Ce, Pr, and Nd), and [K(crypt)][Cp′′3Ln], 2-Ln [Cp′′ = C5H3(SiMe3)2]. The 2-Ln complexes (Ce, Pr, and Nd) were synthesized by reduction of Cp′′3Ln with

  为了评估环戊二烯基配取代在新+2离子的镧系元素的配合物的效果，在反应性和光谱和磁特性的比较已被[K（隐窝）] [CP'之间进行3 LN]，1-LN（CP' = C 5 H ^ 4森达3 ;隐窝= 2.2.2-穴醚; Ln为镧，铈，镨，和Nd）和[K（隐窝）] [CP'' 3 LN]，2-LN [CP'' ＝ C 5 H 3（SiMe 3）2 ]。的2-LN络合物（铈，镨，和Nd）通过还原CP''的合成3Ln在存在隐窝的情况下具有石墨化钾和晶体学特征。的结构和紫外-可见光谱2-LN类似于的1-LN，如所预期，但对于更高的热稳定性2-LN，从比较预期2-U和1-U ，也未观察到。研究了2-Ce和2-Pr的磁化率，因为1-Ce和1-Pr的磁化率与4f n 5d 1电子构型的简单耦合模型不匹配。2-Ln络合物的磁数据类似于1-Ln的磁数据，这表明与后期镧系元素的非传统二价配合物相比，具有4f n 5d
• d/f‐Polypnictides Derived by Non‐Classical Ln ²⁺ Compounds: Synthesis, Small Molecule Activation and Optical Properties
  作者：Niklas Reinfandt、Nadine Michenfelder、Christoph Schoo、Ravi Yadav、Stephan Reichl、Sergey N. Konchenko、Andreas N. Unterreiner、Manfred Scheer、Peter W. Roesky

  DOI：10.1002/chem.202100605

  日期：2021.5.20

  [Cp′′2Ln(E5)FeCp*] (Ln=La, Ce, Nd; E=P, As) were obtained. Their reactivity was studied by activation of P4, resulting in a selective expansion of the P5 rings. The obtained compounds [K(18-crown-6)] [Cp′′2Ln(P7)FeCp*] (Ln=La, Nd) are the first examples of an activation of P4 by a f-element-polypnictide complex. Additionally, the first systematic femtosecond (fs)-spectroscopy investigations of d/f-polypnictides

  迄今为止，由二价镧系元素引起的还原化学主要集中在sa上。考虑到镧系元素的丰富的物理性质，对一种元素的这种限制是一个缺点。由于几乎所有镧系元素的分子二价化合物都已经存在了一段时间，因此我们使用了一种已知的早期镧系元素和两种新的非经典还原剂来建立复杂的还原化学。其结果是，六个新的d / F-polyphosphides或d / F-polyarsenides，[K（18-冠-6）] [CP'' 2 LN（E 5）FeCP *]（Ln为镧，铈，钕;得到E ＝ P，As）。通过活化P 4来研究它们的反应性，从而导致P 5环的选择性膨胀。将所得到的化合物[K（18-冠-6）] [CP'' 2Ln（P 7）FeCP *]（Ln = La，Nd）是通过f元素-多肽复合物激活P 4的第一个例子。此外，首次对d / f-多聚肽进行系统的飞秒（fs）光谱学研究是为了展示获得更广泛的镧系元素化合物所具有的优势。
• Systematic studies on the reactions of lanthanide trichlorides with Na[1,3-bis(trimethylsilyl) cyclopentadienyl]. Crystal structures of [1,3-(Me3Si)2C5H3]3Ln (LnLa, Nd, Gd, Dy)
  作者：Zuowei Xie、Kwoli Chui、Zhixian Liu、Feng Xue、Zeying Zhang、Thomas C.W. Mak、Jie Sun

  DOI：10.1016/s0022-328x(97)00489-0

  日期：1997.12

  Reflux of LnCl(3) with an excess amount of Na[(Me3Si)(2)C5H3] in THF and then in toluene gave two kinds of complexes dependent upon the size of the central metal, the tris ligand complexes of the type [(Me3Si)(2)C5H3](3)Ln (Ln = La, Nd, Sm, Gd or Dy) and the bis ligand complexes of the general formula [(Me3Si)(2)C5H3}(2)LnCl](2) (Ln = Gd, Dy, Y, Er or Yb). Neither THF coordinated nor THF ring-opened product was isolated. These compounds were fully characterized by elemental analyses, IR, MS and H-1 NMR (for diamagnetic metals) spectroscopy. The structures of the tris ligand complexes of La. Nd, Gd and Dy have been further confirmed by single-crystal X-ray diffraction analyses. Each of the three (Me3Si)(2)C5H3 ligands is eta(5)-bonded to the central lanthanide atom to form the trigonal planar geometry with an average (ring centroid)-metal-(ring centroid) bond angle of 120 degrees. The variations in the metal-carbon bond distances are consistent with the phenomenon of lanthanide contraction. (C) 1997 Elsevier Science S.A.