[Cp*RuCl₂(η³-allyl)]

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: [Cp*RuCl₂(η³-allyl)]
• 英文别名: [(η⁵-C₅Me₅)RuCl₂(η³-allyl)]；(η(5)-C5Me5)Ru(η(3)-C3H5)Cl2；π-allyl(dichloro)(pentamethylcyclopentadienyl)ruthenium (IV)；[Ru(IV)(η3-allyl)(η5-C5Me5)Cl2]；[Ru(η3-C3H5)(η5-C5Me5)Cl2]；[Ru(Cp*)(η3-C3H5)Cl2]
• 化学式: C₁₃H₂₀Cl₂Ru
• 分子量: 348.278
• InChiKey: RRSFFBAVMVOZLN-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  5.21
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 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：

  [Cp*RuCl₂(η³-allyl)] 在 HBr 作用下， 以 二氯甲烷 、 水 为溶剂， 以90%的产率得到Ru(η5-C5H5)-(η3-C3H5)Br2
  参考文献：
  名称：

  烯丙基卤化物向钌（II）化合物的氧化加成。钌（IV）-烯丙基配合物的制备，反应和X射线晶体结构

  摘要：

  DOI：

  10.1021/om00117a041
• 作为产物：
  描述：

  (η(5)-C5Me5)Ru(η(3)-C3H5)(CH2Cl)Cl 以 氘代苯 为溶剂， 生成 [Cp*RuCl₂(η³-allyl)]
  参考文献：
  名称：

  Formation and reactivity of the chloromethyl π-allyl complex (η5-C5Me5)Ru(η3-C3H5)(CH2Cl)Cl

  摘要：

  Treatment of (eta(5)-C(5)Me(5))Ru(eta(3)-C3H5)Cl-2 in CH2Cl2 with ethereal diazomethane in the presence of copper powder produces (eta(5)-C(5)Me(5))Ru(eta(3)-C3H5)(CH2Cl)Cl in moderate yield with no detectable formation of the bis(chloromethyl) derivative. Deuterium labeling with CD2N2 shows no methylene scrambling into the allyl ligand. Evidence from NMR spectroscopy supports an endo allyl conformation in the chloromethyl complex. Mass spectroscopy experiments indicate that the d(4) (Ru-IV) metal center is relatively ineffective in stabilizing the [(eta(5)-C(5)Me(5))Ru(eta(3)-C3H5)(= CH2)Cl](+) fragment. The new chloromethyl complex reacts under photochemical conditions to give polymethylene with the regeneration of the starting dichloride. No intramolecular transfer of methylene to the allyl or (eta(5)-C(5)Me(5)) ligands is observed.

  DOI：

  10.1016/0022-328x(94)05073-k

文献信息

• Oxidative Addition of Allylic Substrates to Coordinatively Unsaturated Ruthenium Compounds, [Ru(<i>η</i>⁵-C₅Me₅)(<i>η</i>-amidinate)]: Preparation, Structure Elucidation, and Catalysis of Novel Ruthenium (IV)-<i>η</i>³-Allyl Complexes
  作者：Hideo Kondo、Akira Kageyama、Yoshitaka Yamaguchi、Masa-aki Haga、Karl Kirchner、Hideo Nagashima

  DOI：10.1246/bcsj.74.1927

  日期：2001.10

  coordinative unsaturation, gave novel cationic π-allyl ruthenium(IV) species. The compounds [Ru(η3-allyl)(η5-C5Me5)(η2-amidinate)]+X− were isolated by anion exchange of the products (X = PF6, BF4, BPh4), and were characterized by spectroscopic analysis. The crystallography of two of the [Ru(η3-allyl)(η5-C5Me5)(η2-amidinate)]+X− revealed a four-legged piano stool structure in which two nitrogen atoms in

  烯丙基卤化物、乙酸盐和碳酸盐与 [Ru(η5-C5Me5)(η-脒)] [脒：iPrNC(Me)=NiPr (1a), tBuNC(Ph)=NtBu (1b)] 的氧化加成反应，其中显示出配位不饱和的迹象，产生了新的阳离子 π-烯丙基钌 (IV) 物种。化合物[Ru(η3-烯丙基)(η5-C5Me5)(η2-脒)]+X-通过产物(X = PF6、BF4、BPh4)的阴离子交换分离，并通过光谱分析表征。[Ru(η3-allyl)(η5-C5Me5)(η2-amidinate)]+X− 中两个的晶体学揭示了四足钢琴凳结构，其中脒配体中的两个氮原子和脒配体中的两个碳原子。 η3-烯丙基配体占据四条腿的位置；η3-烯丙基配体的取向是内向的。尽管前体[Ru(η5-C5Me5)(η-脒)]的循环伏安图，表明除烯丙基卤化物之外的有机卤化物可能氧化加成到[Ru(η5-C5Me5)(η-脒)]，只有烯丙基卤
• Fast, efficient Ru(iv)-catalysed regioselective allylation of indoles using allyl alcohol (without additives) under mild conditions
  作者：Alexey B. Zaitsev、Stefan Gruber、Paul S. Pregosin

  DOI：10.1039/b710763c

  日期：——

  The new Ru(IV) salt, [Ru(eta(3)-C(3)H(5))(Cp*)(CH(3)CN)(2)](PF(6))(2), is an excellent catalyst for the regioselective allylation of a variety of indole compounds using allyl alcohol as substrate; there are no co-catalysts required in this chemistry and the yields and reaction conditions are very favorable.

  新的Ru（IV）盐[Ru（eta（3）-C（3）H（5））（Cp *）（CH（3）CN）（2）]（PF（6））（2），是使用烯丙醇作为底物对多种吲哚化合物进行区域选择性烯丙基化的极佳催化剂；在该化学过程中不需要助催化剂，并且产率和反应条件是非常有利的。
• Synthesis and Properties of Diruthenium Tetrahydrides Supported by Less-substituted, Sterically Demanding Poly-<i>tert</i>-butylated Cyclopentadienyls
  作者：Takako Yanagi、Hiroharu Suzuki、Masataka Oishi

  DOI：10.1246/cl.130699

  日期：2013.11.5

  Synthesis of diruthenium tetrahydrido complexes 1 with substituted cyclopentadienyls from readily available ruthenium η3-allyl complexes 3 has been attained by LiEt3BH-mediated reaction followed by conventional protonolysis. Complexes 1d and 1e having 1,2,4-tri- and 1,3-di-tert-butylated cyclopentadienyls obtained by this protocol have sufficient thermal stability in addition to the significant lability of the Ru–H bonds.

  通过LiEt3BH介导的反应，随后进行常规的质子解离，成功合成了与已知的环戊二烯基取代基相结合的二铑四氢化合物1，这些取代基来源于易得的铑η3-烯丙基化合物3。采用该方法合成的复合物1d和1e含有1,2,4-三和1,3-二叔丁基环戊二烯基，不仅具有足够的热稳定性，还显示了Ru–H键的显著活泼性。
• Rapid, Selective Ru-Sulfonate-Catalyzed Allylation of Indoles Using Alcohols as Substrates
  作者：Stefan Gruber、Alexey B. Zaitsev、Michael Wörle、Paul S. Pregosin、Luis F. Veiros

  DOI：10.1021/om900168y

  日期：2009.6.22

  halides, acetates, etc., to be used as substrates in this allylation chemistry, thereby avoiding the use of a (wasted) leaving group. The branched products are favored, and in a number of examples b/l ratios in excess of 20 are observed. The catalyst is selective in that there is little or no N-allylation. The use of acids such as CF3SO3H or HBF4 results in slower and/or less selective reactions. Although

  使用ArCH（OH）CH = CH 2（Ar = Ph，2-CH 3 C 6 H 4，2 -CH 3 OC 6 H 4 2-ClC 6 H 4和1-萘基）在[Ru（Cp *）（CH 3 CN）3 ]（PF 6）+磺酸助催化剂RSO 3 H（R =对甲苯基，樟脑碎片或CH 3）。新的催化剂允许烯丙醇而不是碳酸盐，卤化物，乙酸盐等在该烯丙基化化学反应中用作底物，从而避免使用（浪费的）离去基团。支链产物是有利的，并且在许多实例中，观察到b / l比超过20。该催化剂是选择性的，因为几乎没有或没有N-烯丙基化。使用酸例如CF 3 SO 3 H或HBF 4导致较慢和/或较少的选择性反应。尽管磷酸添加剂显示出一定的前景，但是羧酸的效力低得多或根本不催化反应。预先形成的分离的复合体的[Ru（CP *）（η 3 -C 3 H ^ 5）（RSO 3）2 ]是有效的催化剂前体；然而，NMR实验表明，活性物质中
• Facile Ruthenium(IV)-Catalyzed Single and Double Allylation of Indole Compounds using Alcohols as Substrates: Aspects of Ruthenium(IV) Allyl Chemistry
  作者：Stefan Gruber、Alexey B. Zaitsev、Michael Wörle、Paul S. Pregosin、Luis F. Veiros

  DOI：10.1021/om800295z

  日期：2008.8.1

  [Ru(Cp*)(η3-C3H5)(CH3CN)2](PF6)2 is shown to be an excellent and rapid catalyst for the C-allylation of indole compounds using allyl alcohols as substrates. Selective, one-pot N,C-double allylation is also possible. Preliminary experiments suggest that vinyl epoxides may be used as an allyl source. Stoichiometric reactions of CH2═CHCH(OH)CH═CH2, CH2═CHCH(OAc)CH═CH2, and CH2═CHCH═CHCH2Br with [Ru(Cp*)(CH3CN)3](PF6)

  的双阳离子钌（IV）盐的[Ru（CP *）（η 3 -C 3 H ^ 5）（CH 3 CN）2 ]（PF 6）2被示出为用于吲哚的C-烯丙基化优异的和快速的催化剂烯丙醇为底物的化合物。选择性的一锅N，C-双烯丙基化也是可能的。初步实验表明，乙烯基环氧化合物可以用作烯丙基源。CH的化学计量反应2 = CHCH（OH）CH = CH 2，CH 2 = CHCH（OAC）CH = CH 2，和CH 2 ═CHCH═CHCH 2溴用的[Ru（CP *）（CH 3 CN）3]（PF 6），得到新的钌（IV）η 3 -乙烯基烯丙基盐，其中的两个，的[Ru（CP *）（κ 2 -OAc）（η 3 -乙烯基烯丙基）]（PF 6）（13）和[茹（CP *）溴（η 3 -乙烯基烯丙基）（CH 3 CN）]（PF 6）（14），进行了研究的X射线衍射的方法。除了钌（IV）η 3 -乙烯基烯丙基键合方式，我们还发