(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)-cyclohexane

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)-cyclohexane
• 英文别名: (2,3,4,5-Tetramethylcyclopenta-2,4-dien-1-yl)cyclohexane；(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)cyclohexane
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: WPPRURLZNFWAJM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  五羰基铁 、 (2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)-cyclohexane 以 5,5-dimethyl-1,3-cyclohexadiene 为溶剂， 反应 12.0h， 以89%的产率得到[η⁵-C₅Me₄CH(CH₂)₅Fe(CO)(μ-CO)]₂
  参考文献：
  名称：

  五种基于取代四甲基环戊二烯基配体的双核羰基铁配合物：合成和晶体结构

  摘要：

  用 Fe(CO)5 热处理取代的四甲基环戊二烯 [C5Me4HR] [R = 正丙基 (1)、异丙基 (2)、环戊基 (3)、环己基 (4) 和 4-NMe2Ph (5)]得到五个新的取代四甲基环戊二烯基双核羰基铁配合物，[η5-C5Me4CH2CH2CH3]2Fe2(CO)4(6)，[η5-C5Me4CH(CH3)2]2Fe2(CO)4(7)，[η5-C5Me4CH(CH2)4 ]2Fe2(CO)4 (8)、[η5-C5Me4CH(CH2)5]2Fe2(CO)4 (9) 和 [(η5-C5Me4)(4-NMe2Ph)]2Fe2(CO)4 (10)。新配合物通过元素分析、IR 和 1H NMR 光谱进行了表征。6、8、9和10的分子结构由X射线单晶衍射确定。图形概要

  DOI：

  10.1080/00958972.2013.873533
• 作为产物：
  描述：

  在 盐酸 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 1.0h， 以4.825 g的产率得到(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)-cyclohexane
  参考文献：
  名称：

  Extending the range of pentasubstituted cyclopentadienyl compounds: The synthesis of a series of tetramethyl(alkyl or aryl)cyclopentadienes (Cp ∗ R ), their iridium complexes and their catalytic activity for asymmetric transfer hydrogenation

  摘要：

  Tetramethyl(alky or aryl)cyclopentadienes were synthesized and the organometallic half-sandwich iridium complexes of the form [(eta(5)-Cp*(R))Ir(aa)Cl], Cp*(R) = tetramethyl(phenyl)cyclopentadienyl (Cp*(Ph)), tetramethyl(benzyl)cyclopentadienyl (Cp*(Bn)), tetramethyl(2-propyl)cyclopentadienyl (Cp*(iPr)), or tetramethyl(cyclohexyl)cyclopentadienyl (Cp*(Cy)) were prepared and characterized. The complexes adopt a piano stool configuration, forming diastereomers, with ratios similar to reported [(eta(5)-Cp*(R))Ir(aa)Cl] complexes. The complexes display an intermolecular hydrogen bonding network in the solid state. These complexes were tested for the asymmetric transfer hydrogenation of several ketones, showing that the R of the Cp*(R) drastically impacts both selectivity and rate of reaction. Additionally, severe solvent effects are displayed when the reaction media is changed from aqueous to organic solvent. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2014.06.053

文献信息

• Improved Synthesis of [Cp^RRhCl₂]₂ Complexes
  作者：Mark A. Mantell、Jeff W. Kampf、Melanie Sanford

  DOI：10.1021/acs.organomet.8b00400

  日期：2018.10.8

  communication presents a new preparation for complexes of the general structure [CpRRhCl2]2 (CpR = a substituted cyclopentadienyl ligand). Using isopropyl alcohol as the solvent in place of ethanol prevents the formation of Rh-carbonyl side products during synthesis. This procedure also affords higher yields of many [CpRRhCl2]2 derivatives with significantly shorter reaction times in comparison to previous

  该通报提出了一种通用结构[Cp R RhCl 2 ] 2（Cp R =取代的环戊二烯基配体）的配合物的新制备方法。使用异丙醇代替乙醇作为溶剂可防止在合成过程中形成Rh-羰基副产物。与先前的方法相比，该方法还提供了许多[Cp R RhCl 2 2 ] 2衍生物的更高产率，且反应时间明显缩短。该方法适用于带有空间上不同的环戊二烯基配体的多种配合物。
• Increasing Anticancer Activity with Phosphine Ligation in Zwitterionic Half-Sandwich Iridium(III), Rhodium(III), and Ruthenium(II) Complexes
  作者：Xueyan Hu、Lihua Guo、Mengqi Liu、Qiuya Zhang、Yuwen Gong、Mengru Sun、Shenghan Feng、Youzhi Xu、Yiming Liu、Zhe Liu

  DOI：10.1021/acs.inorgchem.2c03279

  日期：2022.12.12

  The synthesis and biological assessment of neutral or cationic platinum group metal-based anticancer complexes have been extremely studied, whereas there are few reports on the corresponding zwitterionic complexes. Herein, the synthesis, characterization, and bioactivity of zwitterionic half-sandwich phosphine–imine iridium(III), rhodium(III), and ruthenium(II) complexes were presented. The sulfonated

  中性或阳离子铂族金属基抗癌配合物的合成和生物学评价已被大量研究，而相应的两性离子配合物的报道很少。在此，介绍了两性离子半夹心膦-亚胺铱 (III)、铑 (III) 和钌 (II) 配合物的合成、表征和生物活性。磺化膦亚胺配体和一组两性离子半夹心P , N-螯合有机金属配合物通过核磁共振 (NMR)、质谱（电喷雾电离、ESI）、元素分析和 X 射线晶体学进行了全面表征。还确定了这些配合物的溶液稳定性及其光谱特性。值得注意的是，与相应的两性离子吡啶基亚胺N、N-螯合铱 (III) 和钌 (II) 配合物相比，几乎所有这些配合物都显示出对模型 HeLa 和 A549 癌细胞的抗癌活性增强，后者在我们的研究中表现出无活性或低活性之前的工作。这些两性离子P、N的亲脂性和细胞内摄取水平的增加-螯合复合物似乎与其优异的细胞毒性有关。此外，这些复合物显示出与牛血清白蛋白 (BSA) 的生物分子相互作用。流
• Rapid Access to Derivatized, Dimeric, Ring-Substituted Dichloro(cyclopentadienyl)rhodium(III) and Iridium(III) Complexes
  作者：Loren C. Brown、Emily Ressegue、Joseph S. Merola

  DOI：10.1021/acs.organomet.6b00580

  日期：2016.12.27

  The present work describes the design and synthesis of a series of rhodium and iridium dimers [(eta(5)-ring)MCl](2)(mu(2)-Cl)(2) (where (eta(5)-ring)MCl = (eta(5)-Me4C5R)Rh(III)Cl or (eta(5)-Me4C5R)Ir(III)Cl) using a new and efficient 1 h procedure. Rhodium and iridium dimeric complexes were synthesized via a microwave reaction. The modified HMe4C5R (R = isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, phenyl, benzyl, phenethyl, cyclohexyl, and cyclopentyl) type ligands were synthesized by reaction of 2,3,4,S-tetramethylcyclopent-2-en-1-one with the respective Grignard reagent (RMgX), followed by elimination of water under acidic conditions to produce the tetramethyl(alkyl or aryl)cyclopentadienes in moderate to excellent yields (40-98%). Reaction of the HMe4C5R ligands with [M(COD)](mu(2)-Cl)(2) (M = Rh, Ir; COD = 1,S-cyclooctadiene) gave the dimeric complexes [(eta(5)-Me4C5R)MCl](2)(mu(2)-Cl)(2) in yields ranging from 47% to 96%. The derivatized dimers were tested for antimicrobial activity, showing activity against Mycobacterium smegmatis and improved activity with derivatized R groups against Staphylococcus aureus and MRSA 43300. The characterization of these complexes was completed by NMR spectroscopy, single-crystal X-ray diffraction, high-resolution mass spectrometry, and elemental analysis.
• Extending the range of pentasubstituted cyclopentadienyl compounds: The synthesis of a series of tetramethyl(alkyl or aryl)cyclopentadienes (Cp ∗ R ), their iridium complexes and their catalytic activity for asymmetric transfer hydrogenation
  作者：David M. Morris、Michael McGeagh、David De Peña、Joseph S. Merola

  DOI：10.1016/j.poly.2014.06.053

  日期：2014.12

  Tetramethyl(alky or aryl)cyclopentadienes were synthesized and the organometallic half-sandwich iridium complexes of the form [(eta(5)-Cp*(R))Ir(aa)Cl], Cp*(R) = tetramethyl(phenyl)cyclopentadienyl (Cp*(Ph)), tetramethyl(benzyl)cyclopentadienyl (Cp*(Bn)), tetramethyl(2-propyl)cyclopentadienyl (Cp*(iPr)), or tetramethyl(cyclohexyl)cyclopentadienyl (Cp*(Cy)) were prepared and characterized. The complexes adopt a piano stool configuration, forming diastereomers, with ratios similar to reported [(eta(5)-Cp*(R))Ir(aa)Cl] complexes. The complexes display an intermolecular hydrogen bonding network in the solid state. These complexes were tested for the asymmetric transfer hydrogenation of several ketones, showing that the R of the Cp*(R) drastically impacts both selectivity and rate of reaction. Additionally, severe solvent effects are displayed when the reaction media is changed from aqueous to organic solvent. (C) 2014 Elsevier Ltd. All rights reserved.
• Five dinuclear iron carbonyl complexes based on substituted tetramethylcyclopentadienyl ligands: synthesis and crystal structures
  作者：Zhihong Ma、Kaiming Guo、Na Wang、Hong Wang、Zhangang Han、Xuezhong Zheng、Jin Lin

  DOI：10.1080/00958972.2013.873533

  日期：2014.1.2

  ienyl dinuclear iron carbonyl complexes, [η5-C5Me4CH2CH2CH3]2Fe2(CO)4 (6), [η5-C5Me4CH(CH3)2]2Fe2(CO)4 (7), [η5-C5Me4CH(CH2)4]2Fe2(CO)4 (8), [η5-C5Me4CH(CH2)5]2Fe2(CO)4 (9), and [(η5-C5Me4)(4-NMe2Ph)]2Fe2(CO)4 (10). The new complexes were characterized by elemental analysis, IR, and 1H NMR spectra. The molecular structures of 6, 8, 9, and 10 were determined by X-ray single crystal diffraction. Graphical

  用 Fe(CO)5 热处理取代的四甲基环戊二烯 [C5Me4HR] [R = 正丙基 (1)、异丙基 (2)、环戊基 (3)、环己基 (4) 和 4-NMe2Ph (5)]得到五个新的取代四甲基环戊二烯基双核羰基铁配合物，[η5-C5Me4CH2CH2CH3]2Fe2(CO)4(6)，[η5-C5Me4CH(CH3)2]2Fe2(CO)4(7)，[η5-C5Me4CH(CH2)4 ]2Fe2(CO)4 (8)、[η5-C5Me4CH(CH2)5]2Fe2(CO)4 (9) 和 [(η5-C5Me4)(4-NMe2Ph)]2Fe2(CO)4 (10)。新配合物通过元素分析、IR 和 1H NMR 光谱进行了表征。6、8、9和10的分子结构由X射线单晶衍射确定。图形概要