(η5-1-trifluoromethyl-2,3,4,5-tetramethylcyclopentadienyl)tris(acetonitrile)ruthenium hexafluorophosphate | 406502-40-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (η5-1-trifluoromethyl-2,3,4,5-tetramethylcyclopentadienyl)tris(acetonitrile)ruthenium hexafluorophosphate
• 英文别名: [Ru(η5-C5Me4CF3)(MeCN)3][PF6]；[(η⁵-C₅Me₄CF₃)Ru-(NCMe)₃]PF₆；[(η⁵-C₅Me₄CF₃)Ru(NCMe)₃]PF₆；[Ru(η5-trifluoromethyltetramethylcyclopentadienyl)(acetonitrile)3][PF6]；acetonitrile;ruthenium(2+);1,2,3,4-tetramethyl-5-(trifluoromethyl)cyclopenta-1,3-diene;hexafluorophosphate
• CAS: 406502-40-7
• 化学式: C₁₆H₂₁F₃N₃Ru*F₆P
• 分子量: 558.392
• InChiKey: NRMDEAPKKUVTEF-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：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (η5-1-trifluoromethyl-2,3,4,5-tetramethylcyclopentadienyl)tris(acetonitrile)ruthenium hexafluorophosphate 、 三苯基膦 以 二氯甲烷 为溶剂， 以62%的产率得到(η5-1-trifluoromethyl-2,3,4,5-tetramethylcyclopentadienyl)bis(acetonitrile)(triphenylphosphine)ruthenium hexafluorophosphate
  参考文献：
  名称：

  A Facile Route to 1-Trifluoromethyl-2,3,4,5-tetramethylcyclopentadienyl Ruthenium Half- and Mixed-Sandwich Compounds

  摘要：

  A series of half and mixed-sandwich (Cpdouble dagger = 1-trifluoromethyl-2,3,4,5-tetramethylcyclopentadienide) ruthenium compounds have been synthesized from a new Cpdouble daggerRu synthon, [Cpdouble daggerRu(NCCH3)(3)](PF6). [Cpdouble daggerRu(NCCH3)(3)](PF6) is efficiently generated by photolysis of [Cpdouble daggerRuBz](PF6) in acetonitrile with a quantum yield of approximately 0.34. The methods described here should be useful for the synthesis of other compounds that contain the Cpdouble daggerRu group.

  DOI：

  10.1021/om010863g
• 作为产物：
  描述：

  η5-1-trifluoromethyl-2,3,4,5-tetramethylcyclopentadienyl-η6-benzene ruthenium hexafluorophosphate 以 乙腈 为溶剂， 以0%的产率得到(η5-1-trifluoromethyl-2,3,4,5-tetramethylcyclopentadienyl)tris(acetonitrile)ruthenium hexafluorophosphate
  参考文献：
  名称：

  A Facile Route to 1-Trifluoromethyl-2,3,4,5-tetramethylcyclopentadienyl Ruthenium Half- and Mixed-Sandwich Compounds

  摘要：

  A series of half and mixed-sandwich (Cpdouble dagger = 1-trifluoromethyl-2,3,4,5-tetramethylcyclopentadienide) ruthenium compounds have been synthesized from a new Cpdouble daggerRu synthon, [Cpdouble daggerRu(NCCH3)(3)](PF6). [Cpdouble daggerRu(NCCH3)(3)](PF6) is efficiently generated by photolysis of [Cpdouble daggerRuBz](PF6) in acetonitrile with a quantum yield of approximately 0.34. The methods described here should be useful for the synthesis of other compounds that contain the Cpdouble daggerRu group.

  DOI：

  10.1021/om010863g
• 作为试剂：
  描述：

  sodiodimethylmalonate 、 ethyl (E)-hex-2-en-1-yl carbonate 在 (η5-1-trifluoromethyl-2,3,4,5-tetramethylcyclopentadienyl)tris(acetonitrile)ruthenium hexafluorophosphate 作用下， 以 四氢呋喃 为溶剂， 反应 18.0h， 生成 dimethyl 2-(hex-1-en-3-yl)malonate 、 dimethyl 2-hexenylmalonate
  参考文献：
  名称：

  载有大体积五取代环戊二烯基配体的钌配合物和[Ru(η5-C5Me4R)(MeCN)3][PF6]预催化剂在亲核烯丙基取代反应中的评价

  摘要：

  [Ru(η5-C5Me4R)(MeCN)3][PF6] (R = CH2tBu, iPr, tBu, 和 CF3; 2-5) 配合物从适当的环戊二烯和 RuCl3·3H2O 开始，分两步合成。完全取代的钌茂 [Ru(C5Me5)(C5Me4R*)], [Ru(C5Me5)(C5nPr4R*)] {R* = (1R,5S)-6,6-二甲基双环[3.1.1]hept-2-en -2-yl} 和 [Ru(C5Me5)(C5nPr5)] 是通过用相应的环戊二烯基锂盐处理 [Ru(C5Me5)Cl]4 获得的。将配合物 2-5 评估为亲核烯丙基取代反应的催化剂前体，并将结果与​​使用 [Ru(C5Me5)(MeCN)3][PF6] (1) 预催化剂获得的结果进行比较。

  DOI：

  10.1002/ejic.200800295

文献信息

• Stereoselective Formation of η⁶-Arene Ruthenium(II) Complexes via Metal-Triggered Bergman and Hopf Cycloaromatizations
  作者：David M. Hitt、Ryan L. Holland、Kim K. Baldridge、Stephen K. Cope、Joseph M. O’Connor

  DOI：10.1021/acs.organomet.7b00679

  日期：2017.11.13

  diastereoselectivity. X-ray structure determination of several isolated ruthenium arene diastereomers confirms the assigned relative stereochemistry for the major and minor stereoisomeric metal arene products. Arene-binding experiments demonstrate that the observed stereoselectivity does not involve complexation of free arene by ruthenium.

  描述了手性共轭二烯和烯二炔的立体选择性金属介导的环芳构化。对于二烯炔环芳构化，将碳立构中心置于烯丙基位置可得到最高的非对映异构体比率（dr）。观察到的立体选择性取决于炔烃取代基的空间体积，因为用炔丙基甲基代替三甲基甲硅烷基会使dr从56:44增加到80:20。对于这两种烯二炔和dienyne底物，[（η 5 -C 5我5）的Ru（NCMe）3 ] PF 6表现出较大的非对映选择性不小于[（η 5 -C 5 H ^ 5）的Ru（NCMe）3 ] PF 6。出于相同的手性烯二炔基，[（η 5 -C 5我5）的Ru（NCMe）3 ] PF 6产生一个4：1的比例的非对映体产品的芳烃，而这两个[（η 5 -C 5我4 CF 3）的Ru（NCMe）3 ] PF 6和[（η 5 -C 5 H ^ 5）的Ru（NCMe）3 ] PF 6生成1：1的产物混合物，表明辅助配体对非对映选择性具有重要的电子影响
• Hydrogenative Cycloisomerization and Sigmatropic Rearrangement Reactions of Cationic Ruthenium Carbenes Formed by Catalytic Alkyne <i>gem</i> ‐Hydrogenation
  作者：Tobias Biberger、Stephan N. Hess、Markus Leutzsch、Alois Fürstner

  DOI：10.1002/anie.202113827

  日期：2022.2.14

  unprecedented hydrogenation reactions are disclosed, commencing with geminal delivery of both H-atoms of H2 to the triple bond of a propargyl alcohol derivative. When catalyzed with cationic ruthenium complexes, the resulting pianostool carbenes are so “hot” that they are readily intercepted by tethered nucleophiles, resulting in cycloisomerization or [2,3]-sigmatropic rearrangement reactions.

  公开了两个前所未有的氢化反应，首先将H 2的两个H原子成对递送至炔丙醇衍生物的三键。当用阳离子钌配合物催化时，生成的钢琴卡宾非常“热”，很容易被束缚的亲核试剂拦截，导致环异构化或[2,3]-σ重排反应。
• Photoactivated Transition-Metal Triggers for Ambient Temperature Enediyne and Dienyne Cyclization: Ruthenium-η⁶-Naphthalene Complexes
  作者：Pengjin Qin、Stephen K. Cope、Han Steger、Kate M. Veccharelli、Ryan L. Holland、David M. Hitt、Curtis E. Moore、Kim K. Baldridge、Joseph M. O’Connor

  DOI：10.1021/acs.organomet.7b00589

  日期：2017.10.23

  A persistent challenge confronting potential applications of the Bergman cycloaromatization reaction is the development of methods for spatiotemporal control of diradical formation. Photochemical variants (photo-Bergman cycloaromatizations) have thus far met with limited success, failing completely in the case of acyclic enediynes. Here we describe the development of efficient photoactivated transition-metal

  Bergman环芳化反应的潜在应用面临的持续挑战是双基形成时空控制方法的发展。迄今为止，光化学变体（光-Bergman环芳族化）仅获得了有限的成功，在无环烯二炔的情况下完全失败了。在这里，我们描述了有效的光活化过渡金属络合物的发展，该络合物允许在环境温度下时空控制烯二炔环芳烃化。该策略依赖于对空气和水分稳定的钌萘配合物，这些配合物经过萘配体的光化学分解，从而生成烯二炔结合和环芳构化的配位点。在光化学条件下，相同的钌萘配合物也可引发二烯炔环化。
• Homoannular disubstituted ruthenocenes containing a trifluoromethyl(tetramethyl)cyclopentadienyl ligand
  作者：S. V. Safronov、A. A. Pavlov、V. I. Sokolov、A. A. Koridze

  DOI：10.1007/s11172-018-2067-x

  日期：2018.2

  ruthenium complexes [CpFRuCl]n and [CpFRu(MeCN)3]PF6 with substituted pentafulvenes 1,2-(Me2NCH)(CO2Et)C5H3 and 1,3-(Me2NCH)(CO2Et)- C5H3 followed by hydrolysis affords new homoannular disubstituted ruthenocenes 1,2- (CO2Et)(CHO)C5H3}RuCpF and 1,3-(CO2Et)(CHO)C5H3}RuCpF (CpF = C5Me4CF3), re- spectively.

  二价钌配合物 [CpFRuCl]n 和 [CpFRu(MeCN)3]PF6 与取代的五富烯 1,2-(Me2NCH)(CO2Et)C5H3 和 1,3-(Me2NCH)(CO2Et)- 反应，然后水解分别提供了新的同环双取代钌 1,2- (CO2Et)(CHO) }RuCpF 和 1,3-(CO2Et)(CHO) }RuCpF (CpF = C5Me4CF3)。