[RuCl2(3-phenylinden-1-ylidene)-(pyridine)(N,N'-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene)] | 1031262-76-6

• 英文名称: [RuCl2(3-phenylinden-1-ylidene)-(pyridine)(N,N'-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene)]
• 英文别名: [RuCl₂(3-phenylinden-1-ylidene)-(pyridine)(N,N'-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene)]；[RuCl2(1,3-bis(2,4,6-trimethylphenyl)imidazoline-2-ylidene)(3-phenylindenylide-1-ene)(pyridine)]；[RuCl₂(3-phenylinden-1-ylidene)-(pyridine)(SIMes)]；[RuCl₂(Ind)(Py)(SIMes)]；ruthenium(II)(dichloro)(SIMes)(pyridine)(C9H5(Ph))
• CAS: 1031262-76-6
• 化学式: C₄₁H₄₁Cl₂N₃Ru
• 分子量: 747.773
• InChiKey: FREADNLQMOKOIV-UHFFFAOYSA-L

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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安全信息

• WGK Germany：
  3

反应信息

• 作为反应物：
  描述：

  三异丙基亚磷酸酯 、 [RuCl2(3-phenylinden-1-ylidene)-(pyridine)(N,N'-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene)] 以 二氯甲烷 为溶剂， 以84%的产率得到cis-(N,N'-bis[2,4,6-(trimethyl)phenyl]imidazolin-2-ylidene)RuCl₂(triisopropylphosphite)(C₉H₅Ph)
  参考文献：
  名称：

  Synthesis and Reactivity of Ruthenium Phosphite Indenylidene Complexes

  摘要：

  The synthesis of the four olefin metathesis precatalysts Caz-1a-d, featuring the NHC ligand N,N'-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) and four different phosphites (P((OPr)-Pr-i)(3), P(OPh)(3), P(OEt)(3), and P(OMe)(3)), is reported. The complexes are readily synthesized from commercially available [RuCl2(3-phenylinden-1-ylidene)-(pyridine)(SIMes)] (Ind-III) in yields of up to 88%. These complexes adopt an unusual cis configuration between the phosphite and the NHC ligands. NMR experiments and computational studies confirm that the cis complexes are thermodynamically favored in comparison to their trans counterparts. In addition, the isomerization from trans to cis occurs via a mononuclear and non-dissociative mechanism. Among the four precatalysts, cis-Caz-1a, featuring a P((OPr)-Pr-i)(3) ligand, displays the highest activity in ring-closing metathesis and cross-metathesis transformations. Experiments at low catalyst loadings demonstrated the potential of this catalyst, allowing better conversions than with commonly used commercially available precatalysts.

  DOI：

  10.1021/om300703p

文献信息

• RUTHENIUM POLYMERISATION CATALYSTS
  申请人：UNIVERSITY COURT OF THE UNIVERSITY OF ST ANDREWS

  公开号：US20140228563A1

  公开（公告）日：2014-08-14

  Cis and trans ruthenium complexes that can be used as catalysts for ring opening metathesis polymerisation (ROMP) are described. The complexes are generally square pyramidal in nature, having two anionic ligands X. Corresponding cationic complexes where one or both of the anionic ligands X are replaced by a non-co-ordinating anionic ligand are also described. Polymers such as polydicyclopentadiene (PDCPD) can be prepared using the catalysts.

  描述了可以用作环开环醚交换聚合（ROMP）催化剂的顺式和反式钌配合物。这些配合物通常具有两个阴离子配体X，本质上是方锥形的。还描述了相应的阳离子配合物，其中一个或两个阴离子配体X被非配位阴离子配体取代。可以使用这些催化剂制备聚二环戊二烯（PDCPD）等聚合物。
• Oxidation-Triggered Ring-Opening Metathesis Polymerization
  作者：Roman Savka、Sabine Foro、Markus Gallei、Matthias Rehahn、Herbert Plenio

  DOI：10.1002/chem.201300868

  日期：2013.8.5

  determined and show that the oxidation of the ferrocene unit has little effect on the ruthenium environment. Two of the eight new complexes were found to be switchable catalysts, in that the reduced form is inactive in the ring‐opening metathesis polymerization of cis‐cyclooctene (COE), whereas the oxidized complexes produce polyCOE. The other complexes are not switchable catalysts and are either inactive

  通过[RuCl 2（NHC）（Ind）（py）]（NHC = 1,3-双（2,4,6-三甲基苯基咪唑啉）的反应，合成了八种新的N -Hoveyda型配合物，产率为67-92％-2-亚甲基（SIMes）或1,3-二（2,6-二异丙基苯基咪唑啉）-2-亚烷基（SIPr），Ind = 3-苯基茚基-1-烯，py =吡啶带有乙烯基和胺或亚胺取代基的预取代的二茂铁化合物。确定了各配合物的氧化还原电势。在所有络合物中，以铁为中心的氧化反应都在接近E的电位发生= + 0.5V。确定了还原的和相应的氧化的Hoveyda型配合物的晶体结构，表明二茂铁单元的氧化对钌环境影响很小。八个新配合物中的两个被发现是可转换的催化剂，因为还原形式在顺式环辛烯（COE）的开环复分解聚合中是无活性的，而氧化的配合物则产生了聚COE。其他配合物不是可转换的催化剂，并且在还原态和氧化态下都是无活性的或有活性的。
• Pyridine as trigger for chloride isomerisation in chelated ruthenium benzylidene complexes: implications for olefin metathesis
  作者：Michaela Zirngast、Eva Pump、Anita Leitgeb、Jörg H. Albering、Christian Slugovc

  DOI：10.1039/c0cc04897f

  日期：——

  The cationic pyridine adduct of a ruthenium complex bearing a chelating benzylidene and an N-heterocyclic carbene was identified as an intermediate during the activation of cis dichloro species and a novel triggering concept for olefin metathesis catalysts based on cationic species was disclosed.

  在活化顺式二氯物种的过程中，一种带有螯合苯亚甲基和 N-杂环碳烯的钌络合物的阳离子吡啶加合物被确定为中间体，并披露了基于阳离子物种的烯烃偏析催化剂的新型触发概念。