Ru(η4-cisoid-1,3-butadiene)(η4-1,5-COD)(NCMe) | 1253386-81-0

• 英文名称: Ru(η4-cisoid-1,3-butadiene)(η4-1,5-COD)(NCMe)
• 英文别名: acetonitrile(η4-cisoid-1,3-butadiene)(η4-1,5-cyclooctadiene)ruthenium(0)；Ru(η⁴-cisoid-1,3-butadiene)(η⁴-1,5-cyclooctadiene)(NCMe)；Ru(η⁴-cisoid-1,3-butadiene)(η⁴-1,5-COD)(NCMe)；Ru(η(4)-cisoid-1,3-butadiene)(η(4)-1,5-COD)(NCMe)；Ru(η4-butadiene)(η4-1,5-COD)(NCMe)；[ruthenium(0)(η4-cisoid-1,3-butadiene)(η4-1,5-COD)(acetonitrile)]；[Ru(η4-butadiene)(η4-1,5-cyclooctadiene)(MeCN)]
• CAS: 1253386-81-0
• 化学式: C₁₄H₂₁NRu
• 分子量: 304.397
• InChiKey: XMPOOZRWTUSJCR-PHFPKPIQSA-N

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：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  3-甲基-1,2-丁二烯 、 Ru(η4-cisoid-1,3-butadiene)(η4-1,5-COD)(NCMe) 以 苯 为溶剂， 以78%的产率得到
  参考文献：
  名称：

  Stoichiometric Carbon–Carbon Bond Forming Reaction of 1,3-Diene with 1,2-Diene in a Ruthenium(0) Complex

  摘要：

  A stoichiometric reaction of Ru(eta(4)-cisoid-2,3-dimethyl-1,3-butadiene) (eta(4)-1,5-COD)(NCMe) (1a) with ethyl 2,3-butadienoate produces rac-prone,supine-(1S,2R,4S,SR)-1-anti-4-anti-Ru(eta(3):eta(3)-1-ethoxycarbonyl-2-methylidene-4,5-dimethylhex-4-ene-1,6-diyl)(eta(4)-1,5-COD) (2aa) in 90% yield and in 52% isolated yield. The stereochemistry of this and the related products shows prior coordination of the 1,2-diene followed by the nucleophilic attack of the coordinated 1,3-diene, where the Ru(0) complex distinguishes two different orthogonal pi planes and the prostereogenic face, depending on the steric congestion, regardless of their electronic properties.

  DOI：

  10.1021/om300326q
• 作为产物：
  描述：

  (η6-naphthalene)(η4-1,5-cyclooctadiene)ruthenium(0) 、 1,3-丁二烯 、 乙腈 以 乙腈 、 苯 为溶剂， 以34%的产率得到Ru(η4-cisoid-1,3-butadiene)(η4-1,5-COD)(NCMe)
  参考文献：
  名称：

  Synthesis of conjugated diene complexes of ruthenium(0) derived from Ru(η6-naphthalene)(η4-1,5-COD): Z to E isomerisation of coordinated 1,3-pentadiene

  摘要：

  The naphthalene complex of zerovalent ruthenium, [Ru(eta(6)-C10H8)(eta(4)-1,5-COD)] (1), readily reacts with 1,3-dienes in the presence of a ligand (L) to produce complexes [Ru(eta(4)-cisoid-1,3-diene)(eta(4)-1,5-COD)(L)] [1,3-diene butadiene, 2,3-dimethylbutadiene, isoprene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-cyclohexadiene; L = MeCN, (BuCN)-Bu-t, PhCN, NCC6H4CN, CO, (BuNC)-Bu-t, pyridine, P(OMe)(3), P(OPh)(3), PMe3, PEt3, PPh3, PCy3]. The single-crystal X-ray structures of [Ru(eta(4)-cisoid-1,3-butadiene)(eta(4)-1,5-COD)(MeCN)] (2a) and [Ru{eta(4)-(E)-cisoid-1.3-pentadiene}(eta(4)-1,5-COD)(PPh3)}](E-5l) show the expected, approximately square pyramidal geometry about the metal atom, with the auxiliary ligand occupying the axial site. [Ru {eta(4)-(Z)-cisoid-1,3-pentadiene}(eta(4)-1,5-COD)(PPh3)] (Z-5l) irreversibly isomerises to E-5l in benzene-d(6) at 30 degrees C, the reaction obeying a first-order rate law [k = (2.89 +/- 0.06) x 10(-4) s(-1)]. This reaction is significantly retarded by addition of PPh3 suggesting that a vacant site is required for the E/Z isomerisation. (C) 2012 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2012.02.018
• 作为试剂：
  描述：

  丁烯酮 、 1,3-丁二烯 在 Ru(η4-cisoid-1,3-butadiene)(η4-1,5-COD)(NCMe) 作用下， 以 苯 为溶剂， 反应 4.0h， 以85%的产率得到3-cyclohexenyl-2-ethanone
  参考文献：
  名称：

  钌（0）配合物在共轭二烯与共轭羰基之间的化学计量和催化交叉二聚作用：通过氧化偶联机理直接进入不饱和羰基化合物

  摘要：

  研究了共轭二烯和共轭羰基之间的一系列化学计量和催化交叉二聚。（η钌的反应4 - cisoid- 1,3-丁二烯）（η 4 -1,5-二COD）（NCMe）（图2a）与丙烯酸甲酯给出了钌（0）络合物，钌[甲基η 4 - cisoid -（2 ë，4 ë） -庚-2,4-二烯酸乙酯（η 4 -1,5-二COD）（NCMe）（3AA）以97％的产率。用一系列丙烯酸叔丁酯，巴豆酸甲酯，3-丁烯-2-酮和N，N-二甲基丙烯酰胺进行的2a相似处理产生类似的3ac。当（ê）-1,3-戊二烯络合物2d中被用在与丙烯酸甲酯的反应中，支链的偶联产物的Ru [甲基η 4 - cisoid-（2 ë，4 ê）-4- methylhepta -2,4-二烯酸酯]（η 4 -1,5-二COD）（NCMe）（3da- b）的显性产率为65％，在19％的产率线性产物一起获得。在（E）-2，5-二甲基六-1，3-二烯配合物

  DOI：

  10.1021/om300234d

文献信息

• Ru(0)-Catalyzed Straightforward Synthesis of Conjugated Tetraenes: An Approach using Two Internal Alkynes with 1,3-Butadiene
  作者：Sayori Kiyota、Masafumi Hirano

  DOI：10.1021/acs.organomet.7b00801

  日期：2018.1.22

  The Ru(0)-catalyzed straightforward synthesis of conjugated tetraenes has been achieved in up to 85% yield by coupling of 2 equiv of internal alkynes with 1,3-butadiene at room temperature. The stoichiometric reaction of [Ru(η4-cisoid-1,3-butadiene)(η4-1,5-COD)(NCMe)] with 2 equiv of 3-hexyne produces a tetraene complex of Ru(0), [Ru3–6-η4-(3E,5E,7E,9E)-4,9-diethyldodeca-3,5,7,9-tetraene}(η4-1,5-COD)(NCMe)]

  通过在室温下将2个当量的内部炔烃与1,3-丁二烯偶联，可以以高达85％的产率实现Ru（0）催化的共轭四烯的直接合成。的化学计量反应的[Ru（η 4 - cisoid -1,3-丁二烯）（η 4 -1,5-二COD）（NCMe）]与2当量3-己炔的产生复杂的Ru（0）的四烯，[茹3-6-η 4 - （3- ê，5 ë，7 ê，9 ë）-4,9- diethyldodeca -3,5,7,9-四烯}（η 4 -1,5-二COD）（ NCMe）]，产率为98％，通过与1,3-丁二烯接触，以92％的产率释放出共轭四烯配体。
• Cross-dimerisation between different cisoid- and transoid-1,3-dienes at a ruthenium(0) centre
  作者：Masafumi Hirano、Haruka Inoue、Takuya Okamoto、Takao Ueda、Nobuyuki Komine、Sanshiro Komiya、Xian-qi Wang、Martin A. Bennett

  DOI：10.1039/c3nj00429e

  日期：——

  Reaction of [Ru(η4-cisoid-2,3-dimethyl-1,3-butadiene)(η4-1,5-COD)(NCMe)] with 1,3-butadiene gives the chelate bis(allylic)ruthenium(II) complex supine,prone-[Ru(η3:η3-2,3-dimethylocta-2,6-diene-1,8-diyl)(η4-1,5-COD)] (supine,prone-2da) in 75% isolated yield as a result of cross-oxidative coupling between two different 1,3-diene units. The structure of 2da has been established unambiguously using X-ray

  的反应的[Ru（η 4 -cisoid -2,3-二甲基-1,3-丁二烯）（η 4 -1,5-二COD）（NCMe）]与1,3-丁二烯给出了螯合双（烯丙基）合钌（II）配合物仰卧，俯卧-的[Ru（η 3：η 3 -2,3-二甲基辛-2,6-二烯-1,8-二基）（η 4 -1,5- -COD）]（仰卧，俯卧- 2DA）以75％的分离产率作为横氧化偶联的两种不同的1,3-二烯单元之间的结果。2DA的结构已使用X射线晶体学方法明确确定。这提供了直接的证据，表明在钌（0）中心发生的甾体选择性氧化偶联发生在顺式和反式二烯之间。
• Stoichiometric and Catalytic Cross Dimerization between Butadiene and Methyl Acrylate Promoted by a Ruthenium(0) Complex
  作者：Masafumi Hirano、Yasutomo Arai、Nobuyuki Komine、Sanshiro Komiya

  DOI：10.1021/om100822n

  日期：2010.11.22

  acrylate in benzene for 3 h at 6 °C produces Rucisoid-η4-(2E,4E)-(methyl hepta-2,4-dienoate)}(η4-1,5-COD)(NCMe) (2a) in 97% yield. Complex 1a (2 mol %) catalyzes the chemoselective cross dimerization between butadiene and methyl acrylate in benzene to give a mixture of the regioisomers of methyl heptadienoate in 43% yield by the oxidative coupling reaction.

  茹的治疗（η 4 -丁二烯）（η 4 -1,5-二COD）（NCMe）（1A）与苯丙烯酸甲酯3小时在6℃产生的Ru cisoid -η 4 - （2- ê，4 ë） - （甲基庚-2,4-二烯酸酯）}（η 4 -1,5-二COD）（NCMe）（图2a，收率97％）。络合物1a（2mol％）催化丁二烯和丙烯酸甲酯在苯中的化学选择性交叉二聚，通过氧化偶联反应以43％的收率得到庚二烯酸甲酯的区域异构体的混合物。
• Mechanistic insights into catalytic linear cross-dimerization between conjugated dienes and styrenes by a ruthenium(0) complex
  作者：Masafumi Hirano、Takao Ueda、Nobuyuki Komine、Sanshiro Komiya、Saki Nakamura、Hikaru Deguchi、Susumu Kawauchi

  DOI：10.1016/j.jorganchem.2015.08.022

  日期：2015.11

  The mechanistic studies for linear cross-dimerization between 2,3-dimethylbuta-1,3-diene and styrene by a Ru(0) complex, Ru(eta(6)-naphthalene)(eta(4)-1,5-COD) (1), are performed both by kinetic and computational studies. This reaction is basically zero-order to both of the diene and styrene concentrations and first-order to the catalyst concentration. The Hammett plot using p-substituted styrenes gives a linear relationship with a positive slope (rho = +0.482). The deuterium isotope experiment clearly shows the present reaction being a formal 1,4-addition of a C-H bond in styrene to cisoid-1,3-diene. These kinetic studies show the reaction proceeding via oxidative coupling mechanism that is also supported by the DFT calculations. (C) 2015 Elsevier B.V. All rights reserved.