bis(1,2,4-tri-t-butylcyclopentadienyl)cerium chloride | 1002717-01-2

• 英文名称: bis(1,2,4-tri-t-butylcyclopentadienyl)cerium chloride
• 英文别名: Ce(C₅H₂tBu₃-1,2,4)₂(Cl)；Ce(Cp^ttt)₂(Cl)；[(1,2,4-tri-tert-butylcyclopentadienyl)2CeCl]；[(1,2,4-(Me3C)3C5H2)2CeCl]；[1,2,4-(Me3C)3C5H2]2CeCl
• CAS: 1002717-01-2
• 化学式: C₃₄H₅₈CeCl
• 分子量: 642.408
• InChiKey: WFTBCYGQNNTOGC-UHFFFAOYSA-M

计算性质

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

• 作为反应物：
  描述：

  bis(1,2,4-tri-t-butylcyclopentadienyl)cerium chloride 、 叠氮基三甲基硅烷 以 甲苯 为溶剂， 以51%的产率得到[1,2,4-(Me3C)3C5H2]2CeN3
  参考文献：
  名称：

  单体 [1,2,4-(Me3C)3C5H2]2CeH 和 CO 有或没有 H2 的反应：实验和计算研究

  摘要：

  将 CO 添加到甲苯中的 [1,2,4-(Me3C)3C5H2]2CeH,CeH 中产生顺式-(Ce)2(μ-OCHCHO)，其中顺式烯二醇基团桥接两个茂金属片段。顺式烯二醇在 7 个月内在 100 °C 下在 C6D6 中定量异构化为反式烯二醇。当溶剂为戊烷时，会形成 Ce(OCH2)Ce，其中氧亚甲基或甲醛二价阴离子桥接两个茂金属片段。顺式烯二醇被认为是通过将 CO 插入 Ce(OCH2)Ce 的 Ce-C 键中形成的，生成 CeOCH2COCe。顺式烯二醇酯的立体化学由 OCH2CO 片段中的 1,2-氢位移决定，该片段具有相对于卡宾孤对的 OC(H2) 键反周面。桥接氧亚甲基络合物与 H2 反应，但不与 CH4 反应，得到 CeOMe，它也是 CeH 与 CO 和 H2 的混合物反应的产物。氧亚甲基络合物与 CO 反应生成顺式烯二醇络合物。C5H5 模型茂金属的 DFT 计算表明.

  DOI：

  10.1021/ja066482h
• 作为产物：
  描述：

  magnesium bis(1,2,4-tris(tert-butyl)cyclopentadienyl) 、 三氯化铈 以 吡啶 、 甲苯 为溶剂， 以42%的产率得到bis(1,2,4-tri-t-butylcyclopentadienyl)cerium chloride
  参考文献：
  名称：

  单体 [1,2,4-(Me3C)3C5H2]2CeH 和 CO 有或没有 H2 的反应：实验和计算研究

  摘要：

  将 CO 添加到甲苯中的 [1,2,4-(Me3C)3C5H2]2CeH,CeH 中产生顺式-(Ce)2(μ-OCHCHO)，其中顺式烯二醇基团桥接两个茂金属片段。顺式烯二醇在 7 个月内在 100 °C 下在 C6D6 中定量异构化为反式烯二醇。当溶剂为戊烷时，会形成 Ce(OCH2)Ce，其中氧亚甲基或甲醛二价阴离子桥接两个茂金属片段。顺式烯二醇被认为是通过将 CO 插入 Ce(OCH2)Ce 的 Ce-C 键中形成的，生成 CeOCH2COCe。顺式烯二醇酯的立体化学由 OCH2CO 片段中的 1,2-氢位移决定，该片段具有相对于卡宾孤对的 OC(H2) 键反周面。桥接氧亚甲基络合物与 H2 反应，但不与 CH4 反应，得到 CeOMe，它也是 CeH 与 CO 和 H2 的混合物反应的产物。氧亚甲基络合物与 CO 反应生成顺式烯二醇络合物。C5H5 模型茂金属的 DFT 计算表明.

  DOI：

  10.1021/ja066482h

文献信息

• Light Lanthanide Metallocenium Cations Exhibiting Weak Equatorial Anion Interactions
  作者：Jingjing Liu、Daniel Reta、Jake A. Cleghorn、Yu Xuan Yeoh、Fabrizio Ortu、Conrad A. P. Goodwin、Nicholas F. Chilton、David P. Mills

  DOI：10.1002/chem.201901167

  日期：2019.6.7

  parent [Ln(Cpttt )2 (Cl)] (2-Ln) with [H(SiEt3 )2 ][B(C6 F5 )4 ], where the anion binds weakly to the equatorial sites of [Ln(Cpttt )2 ]+ through a single fluorine atom in the solid state. For smaller SmIII , [Sm(Cpttt )2 ][B(C6 F5 )4 ] (1-Sm) is isolated, which like heavier 1-Ln does not exhibit equatorial anion interactions, but the EuIII analogue 1-Eu could not be synthesised due to the facile reduction

  由于茂金属配合物[Dy（Cpttt）2] [B（C6 F5）4]（Cpttt = C5 H2 tBu3 -1,2,4，1-Dy）在60 K处表现出磁滞现象，因此类似的镧系（Ln）配合物具有旨在提供对该非凡属性的见解。我们最近报道了来自Gd-Lu的所有较重Ln的同源[Ln（Cpttt）2] [B（C6 F5）4]（1-Ln）；在本文中，我们将此主题扩展到早期的Ln。我们发现，对于最大的LnIII阳离子，接触离子对[Ln（Cpttt）2 （C6 F5-κ1-F）B（C6 F5）3}]（1-Ln; La-Nd）是从母体[Ln（Cpttt）2（Cl）]（2-Ln）与[H（SiEt3）2] [B（C6 F5）4]，其中阴离子与[Ln（Cpttt）2]的赤道位点弱结合+通过单个氟原子处于固态。对于较小的SmIII，分离出[Sm（Cpttt）2] [B（C6 F5）4]（1-Sm），它与较重的1-Ln
• The reaction of bis(1,2,4-tri-t-butylcyclopentadienyl)ceriumbenzyl, Cp′2CeCH2Ph, with methylhalides: a metathesis reaction that does not proceed by a metathesis transition state
  作者：Evan L. Werkema、Richard A. Andersen、Laurent Maron、Odile Eisenstein

  DOI：10.1039/b918103b

  日期：——

  The experimental reaction between [1,2,4-(Me3C)3C5H2]2CeCH2Ph and CH3X, X = F, Cl, Br, and I, yields the metathetical exchange products, [1,2,4-(Me3C)3C5H2]2CeX and CH3CH2Ph. The reaction is complicated by the equilibrium between the benzyl derivative and the metallacycle [1,2,4-(Me3C)3C5H2][(Me3C)2C5H2C(CH3)2CH2]Ce, plus toluene since the metallacycle reacts with CH3X. Labelling studies show that the methyl group of the methylhalide is transferred intact to the benzyl group. The mechanism, as revealed by DFT calculations on (C5H5)2CeCH2Ph and CH3F, does not proceed by way of a four-center mechanism, a σ-bond metathesis, but by a lower barrier process involving a haptotropic shift of the Cp2Ce fragment so that at the transition state the para-carbon of the benzene ring is attached to the Cp2Ce fragment while the CH2 fragment of the benzyl group attacks CH3F that is activated by coordination to the metal ion. As a result the mechanism is classified as an associative interchange process.

  [1,2,4-(Me3C)3C5H2]2Ce Ph 和 X（X = F、Cl、Br 和 I）之间的实验反应产生了元交换产物 [1,2,4-(Me3C)3C5H2]2CeX 和 Ph。苄基衍生物和金属环 [1,2,4-(Me3C)3C5H2][(Me3C)2C5H2C(CH3)2 ]Ce 以及甲苯之间的平衡使反应变得复杂，因为金属环会与 X 发生反应。标记研究表明，甲基卤化物的甲基完整地转移到了苄基上。通过对 (C5H5)2Ce Ph 和 F 的 DFT 计算发现，该机理不是通过四中心机理（Ï-键元合成）进行的，而是通过涉及 Cp2Ce 片段的触变转移的较低障碍过程进行的，因此在过渡态，苯环的对位碳附着在 Cp2Ce 片段上，而苄基的 CH2 片段攻击因与金属离子配位而活化的 F。因此，该机制被归类为关联交换过程。
• Hydrogen for X-Group Exchange in CH₃X (X = Cl, Br, I, OMe, and NMe₂) by Monomeric [1,2,4-(Me₃C)₃C₅H₂]₂CeH: Experimental and Computational Support for a Carbenoid Mechanism
  作者：Evan L. Werkema、Richard A. Andersen、Ahmed Yahia、Laurent Maron、Odile Eisenstein

  DOI：10.1021/om9001846

  日期：2009.6.8

  The reactions between [1,2,4-(Me3C)(3)C5H2](2)CeH, referred to as Cp'2CeH, and CH3X, where X is Cl, Br, I, OMe, and NMe2, are described. The reactions fall into three distinct classes. Class a, where X = Cl, Br, and I, rapidly form Cp'2CeX and CH4 without formation of identifiable intermediates in the H-1 NMR spectra. Class b, where X = Me, proceeds rapidly to CP'Ce-2(eta(2)-CH2OMe) and H-2 and then to CP'2CeOMe and CH4. The methoxymethyl derivative is sufficiently stable to be isolated and characterized, and it is rapidly converted to Cp'2CeOMe in the presence of BPh3. Class c, where X = NMe2, does not result in formation of Cp'2CeNMe2, but deuterium labeling experiments show that H for D exchange occurs in NMe3. Density functional calculations DFT(B3PW91) on the reaction of (C5H5)(2)CeH, referred to as Cp2CeH, and CH3X show that the barrier for alpha-CH activation, resulting in formation of Cp2Ce(eta(2)-CH2X), proceeds with a relatively low activation barrier (Delta G(double dagger)), but the subsequent ejection of CH2 and trapping by H-2 has a higher barrier; the height of the second barrier lies in the order F, Cl, Br, I < OMe << NMe2, consistent with the experimental studies. The DFT calculations also show that the two-step reaction, which proceeds through a carbenoid intermediate, has a lower barrier than a direct one-step or-bond metathesis mechanism. The reaction of Cp2CeCH2OMe and BPh3 is calculated to be a low-activation barrier process, and the ylide, CH2(+)BPh3(-1), is a transition state and not an intermediate.
• Selectivity in the C–H Activation Reaction of CH₃OSO₂CH₃ with [1,2,4-(Me₃C)₃C₅H₂]₂CeH or [1,2,4-(Me₃C)₃C₅H₂][1,2-(Me₃C)₂-4-(Me₂CCH₂)C₅H₂]Ce: To Choose or Not To Choose
  作者：Evan L. Werkema、Ludovic Castro、Laurent Maron、Odile Eisenstein、Richard A. Andersen

  DOI：10.1021/om200842t

  日期：2012.2.13

  The experimental reaction of [1,2,4-(Me3C)(3)CsH2](2)CeH, Cp'2CeH, and CH3OSO2CH3 begins by alpha-C-H activation of the SCH3 group, forming CP'(2) CeCH2SO2(OCH3), which evolves into CP'2CeOCH3 with elimination of CH2 (and presumably SO2). Prolonged heating of this mixture (days at 60 degrees C) forms Cp'2CeOSO2CH3 and CH3OCH3. The metallacycle [1,2,4-(Me3C)(3)C5H2][1,2-(Me3C)(2)-4-(Me2CCH2)C3H2)Ce, when presented with the choice of C-H bonds in CH3S and CH3O groups, deprotonates both with comparable rates, ultimately forming Cp'(2) CeOCH3 and Cp'2CeOSO2CH3 at 20 degrees C. The experimental studies are illuminated by DFT calculations on the experimental systems, which show that the hydride selects the more acidic CH3S bond, whereas the metallacycle reacts with C-H bonds of both the CH3S and CH3O groups of CH3OSO2CH3. In the metallacycle reaction, the initially formed regioisomers, Cp'2CeCH2SO2(OCH3) and Cp'2CeCH2OSO2CH3, rearrange to the observed products, Cp'2CeOCH3 and Cp'2CeOSO2CH3, respectively, Furthermore, C-H activation at the SCH3 group forms two isomers of Cp'2CeCH2SO2(OCH3) in the reaction of CH3OSO2CH3 with the metallacycle and only one in the reaction with the hydride. The lack of selectivity in the reactions of the metallacycle relative to the hydride is due to the metallacycle's greater thermodynamic advantage and lower energy barriers, which are linked to the higher bond energy of Ce-H relative to Ce-C in the metallacycle.