RuCl₂(η⁴-1,5-cyclooctadiene)(MeCN)₂ | 63625-19-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: RuCl₂(η⁴-1,5-cyclooctadiene)(MeCN)₂
• 英文别名: [RuCl2(acetonitrile)2(COD)]；[RuCl2(1,5-cod)(CH3CN)2]；cis-trans-[RuCl2(NCMe)2(cycloocta-1,5-diene)]；[ruthenium(II)(1,5-cyclooctadiene)(acetonitrile)2Cl2]；RuCl2(η4-(1,5-cyclooctadiene)(acetonitrile)2；[RuCl2(1,5-cyclooctadiene)(acetonitrile)2]；[η4-cyclooctadiene)Ru(MeCN)2Cl2]；[RuCl2(COD)(acetonitrile)2]；Ru(COD)Cl2(MeCN)2；[RuCl2(COD)(MeCN)2]；acetonitrile;(1Z,5Z)-cycloocta-1,5-diene;dichlororuthenium
• CAS: 63625-19-4
• 化学式: C₁₂H₁₈Cl₂N₂Ru
• 分子量: 362.264
• InChiKey: MCSFMQOISXSGRH-XRGHXPOKSA-L

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：

  cis-5,15-bis(o-{2-nicotinoylamido}phenyl)-2,8,12,18-tetraethyl-3,7,13,17-tetramethylporphyrinato nickel(II) 、 RuCl₂(η⁴-1,5-cyclooctadiene)(MeCN)₂ 以 氯仿 为溶剂， 以75%的产率得到[NiRuCl2(η4-(1,5-cyclooctadiene)(di[o-nicotinoylphenyl]etioporphyrin)]*H2O
  参考文献：
  名称：

  金属卟啉作为有机金属配合物中的配体：1,5-环辛二烯二氯钌（II）镍（II）卟啉配合物的合成与表征

  摘要：

  已开发出一种利用多螯合卟啉配体α，α- 5,15-双（邻烟碱酰基苯基）-2,8,12,18-四乙基-3,7,13， 17 tetramethylporphyrin，H 2 [DPE] - （PY）2（d I [ ø -nicotinoyl p苯基] ë tioporphyrin）。除卟啉位点外，配体的两个末端吡啶基团还用作另外的螯合物。这两个金属结合位点在化学上是不同的，可用于结合不同的金属中心。通过制备异双金属配合物[Ni（DPE）-（py 2）] Ru（COD）Cl 2证明了该配体的多功能性由与有机金属片段连接的卟啉配位配合物组成。

  DOI：

  10.1016/j.jorganchem.2005.07.030
• 作为产物：
  描述：

  乙腈 、 [Ru(COD)Cl₂]_n 反应 24.0h， 生成 RuCl₂(η⁴-1,5-cyclooctadiene)(MeCN)₂
  参考文献：
  名称：

  Fulvene–Ruthenium and Cp–Ruthenium Complexes via [2 + 2 + 1] Cyclotrimerization of Phenylacetylene with [RuCl(Tp)(1,5-cod)]

  摘要：

  The complex [RuCl(Tp)(1,5-cod)], which bears the labile 1,5-cod ligand, was prepared from a high-yielding route involving the reaction of [RuCl2(1,5-cod)(CH3CN)(2)] with KTp (Tp = HB(pz)(3)). The reaction of [RuCl(Tp)(1,5-cod)] with phenylacetylene in either ethanol or methanol gave anti-Markovnikov alkoxide-adduct complexes [Ru(Tp)(?6-C(5)H2Ph2-CH(Ph)R)] (R = OMe, OEt). These adducts were formed by [2 + 2 + 1] cyclotrimerization reactions of phenylacetylene mediated by the precursor complex, [RuCl(Tp)(1,5-cod)]. The ruthenium(II)fulvene complex, [Ru(Tp)(eta(6)-C(5)H2Ph2-CH(Ph))](+), involved in these transformations was successfully isolated in the presence of NH(4)PF6. These complexes were fully characterized by H-1 NMR, 13C NMR, DEPT, HSQC, IR, and ESI-MS spectroscopy. The molecular structures of [Ru(Tp)(eta(6)-C5H2Ph2-CH(Ph)R)] (R = OMe/OEt) and [Ru(Tp)(eta(6)-C5H2Ph2-CH(Ph))]PF6 have been determined by X-ray single-crystal diffraction. These complexes have piano-stool structures around the ruthenium center where half of the coordination sites are occupied by the pyrazole ligand while the remaining sites are occupied by either the p-bonded cyclopentadiene (Cp) or fulvene ligand.

  DOI：

  10.1021/om500432w
• 作为试剂：
  描述：

  2-Allyl-2-(4,4-dimethyl-cyclohex-2-enyl)-malonic acid dimethyl ester 在 RuCl₂(η⁴-1,5-cyclooctadiene)(MeCN)₂ 作用下， 以 异丙醇 为溶剂， 反应 24.0h， 生成 5,5-Dimethyl-3-methylene-octahydro-indene-1,1-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Ruthenium(II)-Catalyzed Isomer-Selective Cyclization of 1,6-Dienes Leading to exo-Methylenecyclopentanes:  Unprecedented Cycloisomerization Mechanism Involving Ruthenacyclopentane(hydrido) Intermediate

  摘要：

  In the presence of a catalytic amount of ruthenium(II) complexes, [RuCl2(cod)](n), RuCl2(cod)(MeCN)(2), [RuCl2(nbd)](n). [RuCl2(CO)(3)](2), and Cp*Ru(cod)Cl, 1,6-dienes were effectively converted into the corresponding exo-methylenecyclopentanes in good to excellent yields with good isomer purity in i-PrOH at 90 degreesC. The alcoholic solvent was essential for the present catalytic cyclization, and the efficiency increased in the following order: t-BuOH << EtOH less than or equal to i-PrOH. In contrast, a Ru(0) complex. (C6Me6)Ru(cod), catalyzed the cycloisomerization only in 1,2-dichloroethane. The unusual isomer-selectivity occurred when a 1,7-octadiene was subjected to cyclization to give a similar exo-methylenecyclopentane isomer as the major product. The identical isomer selectivity was observed for the cyclization of unsymmetrical 1,6-dienes having one terminal- and one internal-alkene termini. On the basis of the results from the studies using the known ruthenium hydrides and deuterium-labeling substrates, the novel mechanism via the Ru(II) <--> Ru(IV) system involving a ruthenacyclopentane(hydrido) intermediate was proposed, which better explains the particular regiochemistry of the present cyclization than other previous mechanisms.

  DOI：

  10.1021/ja010134s

文献信息

• Substituted tertiary phosphine Ru(II) organometallics: Catalytic utility on the hydrolysis of etofibrate in pharmaceuticals
  作者：P. Muralidhar Reddy、Kanne Shanker、Rondla Rohini、M. Sarangapani、Vadde Ravinder

  DOI：10.1016/j.saa.2007.11.001

  日期：2008.10

  Some new organometallics of ruthenium(II) of the type [RuCl2(COD)(CO)L] (1a-f) and [RuCl2(COD)L2] (2a-f) (where L is substituted tertiary phosphines), have been synthesized by using precursors [RuCl2(COD)(CO)(CH3CN)] (1) and [RuCl2(COD)(CH3CN)2] (2) with the substituted tertiary phosphine ligands in 1:1 and 1:2 molar ratio. The organometallics (2a-f) have been further reacted with carbonmonoxide to

  [RuCL2（COD）（CO）L]（1a-f）和[RuCL2（COD）L2]（2a-f）（其中L是取代的叔膦）类型的钌（II）的一些新有机金属通过使用前体[RuCL2（COD）（CO）（CH3CN）]（1）和[RuCL2（COD）（CH3CN）2]（2）与取代的叔膦配体以1：1和1：2摩尔比合成。使有机金属（2a-f）与一氧化碳进一步反应，以生产[RuCL2（CO）L2]类型的化合物（3a-f）。这些化合物的特征在于元素分析，IR，NMR（1H，13C和31P），质量和电子光谱数据。对所有这些有机金属的催化活性进行了研究，发现它们是依托贝特水解的有效催化剂。通过柱色谱分离水解产物，发现产率百分比为98.6-99.1％。
• Structure and mechanism in aerobic alkene epoxidations promoted by ruthenium complexes of bis(dihydrooxazole) ligands
  作者：Simon Bennett、Stephen M. Brown、Gr�inne Conole、Margalith Kessler、Simon Rowling、Ekkehard Sinn、Simon Woodward

  DOI：10.1039/dt9950000367

  日期：——

  distorted and this is borne out by crystallographic comparison of the model complexes cis-[W(CO)4(S,S)-R2C([graphic omitted])2}](R = H or Me). Mechanistic studies of the epoxidation of styrene and stilbenes in the presence of isobutyraldehyde and molecular oxygen using the ruthenium complexes as catalysts in the presence and absence of 4-tert-butylcatechol as a radical trap revealed that the metals act

  [RuCl 2（NCMe）2（cod）]与双（二氢恶唑）反应，得到[RuCl 2（cod）（S，S）-R 1 2 C-（[省略图示]）2 }]（cod =环辛-1,5-二烯; R 1 = H，R 2 = CH 2的pH值或镨我; R 1 =我，R 2 = PR我）。苄基配合物已经在晶体学上进行了表征。六甲基取代的化合物的配合物的红外光谱表明，配体相对失真，这是通过模型配合物顺式的晶体学比较证实的。-[W（CO）4 （S，S）-R 2 C（[省略图形]）2 }]（R = H或Me）。在存在和不存在4-叔丁基邻苯二酚作为自由基捕集剂的情况下，使用钌配合物作为催化剂，在异丁醛和分子氧存在下，苯乙烯和苯乙烯的环氧化机理研究表明，金属可作为促进Pr生成的促进剂我CO 3 H和这进行环氧化，或者直接或者通过形成氧代-钌物种。
• Reactions of ruthenium(II) tris(pyrazolyl)borate and tris(pyrazolyl)methane complexes with diphenylvinylphosphine and 3,4-dimethyl-1-phenylphosphole
  作者：Dee C Wilson、John H Nelson

  DOI：10.1016/j.jorganchem.2003.07.010

  日期：2003.10

  ruthenium(II) tris(pyrazolyl)borate and tris(pyrazolyl)methane complexes containing diphenylvinylphosphine (DPVP), 3,4-dimethyl-1-phenylphosphole (DMPP) and 1,2-bis (diphenylphosphino) ethane (dppe), namely: (Tp)Ru (DPVP) (CH3CN)Cl; (Tp)Ru (DPVP)2Cl; (Tp)Ru (DPVP) (DMPP) [4+2]Cl; [(Tp)Ru (DPVP)2 (CH3CN)]PF6; (Tp)Ru (DMPP)2 [4+2]Cl; [(Tpm)Ru (DPVP)2 Cl]PF6; [(Tpm)Ru(dppe)Cl]PF6; [(Tpm)Ru(DMPP)2 [4+2]Cl]PF6

  几种新的三（吡唑基）硼酸钌（II）和三（吡唑基）甲烷络合物，其中含有二苯基乙烯基膦（DPVP），3,4-二甲基-1-苯基膦（DMPP）和1,2-双（二苯基膦基）乙烷（dppe），即：（Tp）Ru（DPVP）（CH 3 CN）Cl；（Tp）Ru（DPVP）2 Cl; （Tp）Ru（DPVP）（DMPP）[4 + 2] Cl; [（Tp）Ru（DPVP）2（CH 3 CN）] PF 6；（Tp）Ru（DMPP）2 [4 + 2] Cl; [（Tpm）Ru（DPVP）2 Cl] PF 6；[（Tpm）Ru（dppe）Cl] PF 6；[（Tpm）Ru（DMPP）2 [4 + 2] Cl] PF 6和[（Tp）Ru（dppe）（Me 2 CO）] PF 6已经制备，表征并研究了它们的反应化学。表征包括红外光谱，1 H-，13 C 1 H}-和31 P 1 H} -NMR光谱，在某些情况下还包括X射线晶体学。
• Ruthenium(II) Dichloride Complexes of Chiral, Tetradentate Aminosulfoxide Ligands: Stereoisomerism and Redox-Induced Linkage Isomerism
  作者：Peter O. Atolagbe、Krista N. Taylor、Samantha E. Wood、Arnold L. Rheingold、Lenora K. Harper、Craig A. Bayse、Tim J. Brunker

  DOI：10.1021/ic302188y

  日期：2013.2.4

  each ligand, whereas the trans and cis-α geometric isomers were significant components for one ligand only. Cyclic voltammetry studies show that only the cis-β isomers undergo linkage isomerism upon oxidation to ruthenium(III), whereas the trans and cis-α isomers show simple reversible redox couples.

  合成了两个手性四齿氨基亚砜配体的二氯化钌（II）配合物，仅在N–N连接体上有所不同。对于每个配体，会形成两个主要的异构体，并通过NMR和UV-可见光谱，X射线晶体学和密度泛函理论计算的组合对它们进行结构分配和表征。所述顺式-β几何异构体是由每个配体形成，而反式和顺式-α几何异构体是对一个配体仅显著组件。循环伏安研究表明，只有顺-β异构体在氧化发生键合异构钌（III），而反式与顺-α异构体显示简单的可逆氧化还原对。
• Syntheses and X-ray crystal structures of two ruthenium(II) complexes derived from acetonitrile and dimethylphenylphosphonite
  作者：Samson O. Owalude、Ezekiel O. Odebunmi、Uche B. Eke、Arnold L. Rheingold、Naftali Opembe、Steven L. Suib

  DOI：10.1016/j.jorganchem.2013.04.015

  日期：2013.9

  The ruthenium acetonitrile complex [RuCl2(NCCH3)2P(OCH3)2C6H5}2] (1) and the stable salt [Ru(CH3CN)4P(OCH3)2C6H5}2][BF4]2 (2) have been prepared from [RuCl2(NCCH3)2(COD)] and the salt [Ru(COD)(CH3CN)4][BF4]2 respectively. The two compounds have been characterized by IR, microanalytical, NMR measurements and single-crystal X-ray diffraction studies. The ruthenium in both compounds has almost ideal

  钌乙腈络合物[RuCl 2（NCCH 3）2 P（OCH 3）2 C 6 H 5 } 2 ]（1）和稳定的盐[Ru（CH 3 CN）4 P（OCH 3）2 C 6 H 5 } 2 ] [BF 4 ] 2（2）由[RuCl 2（NCCH 3）2（COD）]和盐[Ru（COD）（CH 3 CN）4 ] [BF 4] 2。通过红外光谱，显微分析，NMR测量和单晶X射线衍射研究对这两种化合物进行了表征。两种化合物中的钌均具有几乎理想的八面体配位几何形状。其中一种络合物[RuCl 2 P（OCH 3）2 C 6 H 5 } 2（NCCH 3）2 ]（1）已显示出对简单酮转移氢化的显着催化活性，而另一种络合物[Ru P （OCH 3）2 C 6 H 5 } 2（NCCH 3）4 ] [BF 4 ] 2（2）对该反应未显示任何催化活性。