Ru(η4-cisoid-2,3-dimethyl-1,3-butadiene)(η4-1,5-COD)(NCMe) | 142084-90-0

• 英文名称: Ru(η4-cisoid-2,3-dimethyl-1,3-butadiene)(η4-1,5-COD)(NCMe)
• 英文别名: acetonitrile(η4-cisoid-2,3-dimethyl-1,3-butadiene)(η4-1,5-cyclooctadiene)ruthenium(0)；ruthenium(0)(η4-2,3-dimethylbutadiene)(η4-1,5-cyclooctadiene)(acetonitrile)；Ru(η⁴-cisoid-2,3-dimethyl-1,3-butadiene)(η⁴-1,5-COD)(NCMe)；[Ru(η⁴-2,3-dimethyl-1,3-butadiene)(η⁴-1,5-COD)-(NCMe)]；[ruthenium(0)(η4-cisoid-2,3-dimethylbutadiene)(η4-1,5-COD)(acetonitrile)]；Ru(η4-cisoid-2,3-dimethyl-1,3-butadiene)(η4-1,5-cyclooctadiene)(MeCN)
• CAS: 142084-90-0
• 化学式: C₁₆H₂₅NRu
• 分子量: 332.451
• InChiKey: RKOPHAYVNALRDG-PHFPKPIQSA-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：

  Ru(η4-cisoid-2,3-dimethyl-1,3-butadiene)(η4-1,5-COD)(NCMe) 在 三甲基膦 作用下， 生成 [ruthenium(0)(η4-cisoid-2,3-dimethylbutadiene)(η4-1,5-COD)(PEt3)]
  参考文献：
  名称：

  Synthesis and protonation of new 1,3-diene complexes of zerovalent ruthenium

  摘要：

  Complexes of general formula Ru(eta-4-1,3-diene)(eta-4-1,5-cyclooctadiene)(nitrile) are formed by reaction of various acyclic 1,3-dienes with Ru(eta-6-naphthalene)(eta-4-1,5-cyclooctadiene) (1) in the presence of nitriles. The coordinated nitrile is readily replaced by stronger pi-acceptors such as CO, (t)BuNC, P(OMe)3 and tertiary phosphines. In contrast, 1,3-cyclohexadiene reacts with 1 in the presence of benzonitrile to give Ru(1,3-C6H8)2(NCPh). The mono-protonated salt obtained from the 2,3-dimethylbutadiene complex Ru(eta-4-C6H10)(eta-4-1,5-C8H12)(PEt3) and HPF6 contains an agostic methyl group whose rotation is almost frozen at -90-degrees-C.

  DOI：

  10.1016/0022-328x(92)83244-c
• 作为产物：
  描述：

  (η6-naphthalene)(η4-1,5-cyclooctadiene)ruthenium(0) 、 2,3-二甲基-1,3-丁二烯 、 乙腈 以 乙腈 、 苯 为溶剂， 以33%的产率得到Ru(η4-cisoid-2,3-dimethyl-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

文献信息

• Stoichiometric and Catalytic Cross Dimerization between Conjugated Dienes and Conjugated Carbonyls by a Ruthenium(0) Complex: Straightforward Access to Unsaturated Carbonyl Compounds by an Oxidative Coupling Mechanism
  作者：Masafumi Hirano、Yasutomo Arai、Yuka Hamamura、Nobuyuki Komine、Sanshiro Komiya

  DOI：10.1021/om300234d

  日期：2012.5.28

  and catalytic cross dimerizations between conjugated dienes and conjugated carbonyls are studied. The reaction of Ru(η4-cisoid-1,3-butadiene)(η4-1,5-COD)(NCMe) (2a) with methyl acrylate gives a Ru(0) complex, Ru[methyl η4-cisoid-(2E,4E)-hepta-2,4-dienoate](η4-1,5-COD)(NCMe) (3aa) in 97% yield. Similar treatments of 2a with a series of tert-butyl acrylate, methyl crotonate, 3-buten-2-one, and N,N-dimethylacrylamide

  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
• 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 formation of conjugated dienyl ketones from 1,3-dienes and ketenes at a ruthenium(0) centre
  作者：Masafumi Hirano、Takuya Okamoto、Nobuyuki Komine、Sanshiro Komiya

  DOI：10.1039/c4nj01001a

  日期：——

  stoichiometric reaction of [Ru(η4-2,3-dimethyl-1,3-butadiene)(η4-1,5-COD)(NCMe)] (1a) with diphenylketene at room temperature produces a new zero-valent complex [Ru(η4-4,5-dimethyl-1,1-diphenylhexa-3,5-diene-2-one)(η4-1,5-COD)(NCMe)] (2aa) in 92% yield. This is the first example of conjugated dienyl ketone formation from 1,3-dienes and ketene. Similarly, the treatment of 1a with ethylphenylketene produces

  的化学计量反应的[Ru（η 4 -2,3-二甲基-1,3-丁二烯）（η 4 -1,5-二COD）（NCMe）]（1A）在室温下用二苯基乙烯酮产生一个新的零价复杂的[Ru（η 4 -4,5-二甲基-1,1-二diphenylhexa -3,5-二烯-2-酮）（η 4 -1,5-二COD）（NCMe）]（2AA）以92％的产率。这是由1，3-二烯和乙烯酮形成共轭二烯基酮的第一个例子。类似地，用乙基苯乙烯酮处理1a可以77％的收率得到脱羰基偶联产物（Z）-5-烷基-2,3-二甲基-5-苯基庚基-1,4-二烯（5）。
• Stoichiometric Carbon–Carbon Bond Forming Reaction of 1,3-Diene with 1,2-Diene in a Ruthenium(0) Complex
  作者：Masafumi Hirano、Takuya Okamoto、Nobuyuki Komine、Sanshiro Komiya

  DOI：10.1021/om300326q

  日期：2012.7.9

  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.