bis(1,2,4-tri-tert-butylcyclopentadienyl)cerium fluoride | 832076-20-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: bis(1,2,4-tri-tert-butylcyclopentadienyl)cerium fluoride
• 英文别名: (1,3,4-tri-tert-butylcyclopentadienyl)2CeF；[1,2,4-(Me3C)3C5H2]2CeF；[(1,2,4-tri-tert-butylcyclopentadienyl)2CeF]；cerium(3+);1,3,5-tritert-butylcyclopenta-1,3-diene;2,3,5-tritert-butylcyclopenta-1,3-diene;fluoride
• CAS: 832076-20-7
• 化学式: C₃₄H₅₈CeF
• 分子量: 625.953
• InChiKey: FCWXJOUJKSXPCY-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  7.6
• 重原子数：
  36
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  bis(1,2,4-tri-tert-butylcyclopentadienyl)cerium fluoride 、 三氟甲烷磺酸甲酯 以 全氘代环己烷 为溶剂， 反应 120.0h， 生成 bis(1,2,4-tri-tert-butylcyclopentadienyl)cerium OSO2CF3
  参考文献：
  名称：

  Cleaving bonds in CH₃OSO₂CF₃with [1,2,4-(Me₃C)₃C₅H₂]₂CeH; an experimental and computational study

  摘要：

  这是一项关于金属茂镧系氢化物[1,2,4-(Me3C)3C5H2]2CeH与甲基三氟甲磺酸酯(CH3OSO2CF3)在20°C下的反应研究。主要发现如下： 1. 反应生成了双金属配合物，其中SO32-阴离子桥连两个金属茂片段，这在有机金属化学中是独特的。 2. 与CH3OSO2CH3相比，CH3OSO2CF3形成类似的产物，但反应速率更快。 3. 该双金属配合物在20°C时的1H NMR谱图显示流动性，低温谱图与固态观察到的构型一致。 4. DFT计算表明，CH3OSO2CF3与金属茂反应时，C-H键活化和直接CH3基团转移具有相似的活化能垒。 5. 这与CH3OSO2CH3的反应不同，后者倾向于在SCH3基团发生C-H键活化。 6. 有趣的是，CH3OSO2CH3和CH3OSO2CF3的C-O键断裂活化能垒相似，这表明传统观点可能过分强调了CF3基团的电子吸引能力对磺酸酯化学和物理性质的影响。 这个研究揭示了反应机理并不是简单的甲基转移，而是涉及更复杂的过程。

  DOI：

  10.1039/c2nj40624a
• 作为产物：
  描述：

  [1,2,4-(Me3C)3C5H2]2Ce(2,3,4-C6H2F3) 以 全氘代环己烷 为溶剂， 生成 bis(1,2,4-tri-tert-butylcyclopentadienyl)cerium fluoride
  参考文献：
  名称：

  Fluorine for Hydrogen Exchange in the Hydrofluorobenzene Derivatives C₆H_xF_(6-x), where x = 2, 3, 4 and 5 by Monomeric [1,2,4-(Me₃C)₃C₅H₂]₂CeH: The Solid State Isomerization of [1,2,4-(Me₃C)₃C₅H₂]₂Ce(2,3,4,5-C₆HF₄) to [1,2,4-(Me₃C)₃C₅H₂]₂Ce(2,3,4,6-C₆HF₄)

  摘要：

  The reaction between monomeric bis(1,2,4-tri-tert-butylcyclopentadienyl)cerium hydride, CP'2CeH, and several hydrofluorobenzene derivatives is described. The aryl derivatives that are the primary products, CP'Ce-2(C6H5-xFx) where x = 1,2,3,4, are thermally stable enough to be isolated in only two cases, since all of them decompose at different rates to CP'2CeF and a fluorobenzyne; the latter is trapped by either solvent when C6D6 is used or by a Cp'H ring when C6D12 is the solvent. The trapped products are identified by GC/MS analysis after hydrolysis. The aryl derivatives are generated cleanly by reaction of the metallacycle, Cp'((Me3C)(2)C5H2C(Me-2)CH2)Ce, with a hydrofluorobenzene, and the resulting arylcerium products, in each case, are identified by their H-1 and F-19 NMR spectra at 20 degrees C. The stereochemical principle that evolves from these studies is that the thermodynamic isomer is the one in which the CeC bond is flanked by two ortho-CF bonds. This orientation is suggested to arise from the negative charge that is localized on the ipso-carbon atom due to C-o(delta+)F-o(delta-) polarization. The preferred regioisomer is determined by thermodynamic rather than kinetic effects; this is illustrated by the quantitative, irreversible solid-state conversion at 25 degrees C over two months of CP'Ce-2(2,3,4,5-C6HF4) to CP'Ce-2(2,3,4,6-C6HF4), an isomerization that involves a CeC(ipso) for C(ortho)F site exchange.

  DOI：

  10.1021/ja800639f

文献信息

• 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 Fluorine Exchange in CH₄_-<i>_x</i>F<i>_x</i> by Monomeric [1,2,4-(Me₃C)₃C₅H₂]₂CeH:  Experimental and Computational Studies
  作者：Evan L. Werkema、Elsa Messines、Lionel Perrin、Laurent Maron、Odile Eisenstein、Richard A. Andersen

  DOI：10.1021/ja0504800

  日期：2005.6.1

  The monomeric metallocenecerium hydride, CP'(CeH (Cp' = 1,2,4-tri-tert-butylcyclopentadienyl), reacts instantaneously with CH)(F, but slower with CH)(F)(, to give CP')(CeF and CH)(2)(3)(2)(2)(2)(4) (in each case, a net H for F exchange reaction. The hydride reacts very slowly with CHF)(, and not at all with CF)(, to give CP'2CeF, H)(, and 1,2,4- and 1,3,5-tri-tert-butylbenzene. The substituted benzenes are postulated to result from trapping of a fluorocarbene fragment derived by a-fluoride abstraction from Cp')(CeCF)(. The fluoroalkyl, Cp')(CeCF)(, is generated by reaction of CP')(CeH and Me)(SiCF)(3)(4)(2)(2)(3)(2)(3)(2)(3)(3) (or by reaction of the metallacycle, [(Cp')(Me)(C))(C)(H)(C(Me)()CH)(]Ce, with CHF)(, and its existence is inferred from the products of decomposition, which are Cp)(CeF, the isomeric tri-tert-butylbenzenes and in the case of Me)(SiCF)(, Me)(SiH. The fluoroalkyls, CP')(CeCH)(F and CP')(CeCHF)(, generated from the metallacycle and CH)(F and CH)(F)(, respectively, are also inferred by their decomposition products, which are CP')(CeF, CH)(, and CHF, respectively, which are trapped. DFT(B3PW91) calculations have been carried out to examine several reaction paths that involve CH and CF bond activation. The calculations show that the CH activation by CP)(CeH proceeds with a low barrier. The carbene ejection and trapping by H)(3)(2)(5)(2)(2)(2)(3)(2)(3)(3)(3)(2)(2)(2)(2)(3)(2)(2)(2)(2)(2)(2) (is the rate-determining step, and the barrier parallels that found for reaction of H)(2) (with CH)(, CHF, and CF)(2)(2). The barrier of the rate-determining step is raised as the number of fluorines increases, while that of the CH activation path is lowered as the number of fluorines increases, which parallels the acidity.
• 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.
• Hydrogen for Fluorine Exchange in C₆F₆ and C₆F₅H by Monomeric [1,3,4-(Me₃C)₃C₅H₂]₂CeH:  Experimental and Computational Studies
  作者：Laurent Maron、Evan L. Werkema、Lionel Perrin、Odile Eisenstein、Richard A. Andersen

  DOI：10.1021/ja0451012

  日期：2005.1.1

  The net reaction of monomeric CP'2CeH [Cp' = 1,3,4-(Me3C)(3)(C5H2)] in C6D6 with C6F6 is CP'2CeF, H-2, and tetrafluorobenzyne. The pentafluoropheny/metallocene, CP'Ce-2(C6F5), is formed as an intermediate that decomposes slowly to CP'2CeF and C6F4 (tetrafluorobenzyne), and the latter is trapped by the solvent C6D6 as a [2+4] cycloadcluct. In C6F5H, the final products are also CP'2CeF and H-2, which are formed from the intermediates CP'Ce-2(C6F5) and CP'Ce-2(2,3,5,6-C6F4H) and from an unidentified metallocene of cerium and the [2+4] cycloadducts of tetra- and trifluorobenzyne with C6D6. The hydride, fluoride, and pentafluoropheny/metallocenes are isolated and characterized by X-ray crystallography. DFT(B3PW91) calculations have been used to explore the pathways leading to the observed products of the exergonic reactions. A key step is a H/F exchange reaction which transforms C6F6 and the cerium hydride into C6F5H and CP'2CeF. This reaction starts by an eta(1)-F-C6F5 interaction, which serves as a hook. The reaction proceeds via a sigma bond metathesis where the fluorine ortho to the hook migrates toward H with a relatively low activation energy. All products observed experimentally are accommodated by pathways that involve C-F and C-H bond cleavages.