[bis(2-methylallyl)cycloocta-1,5-diene]ruthenium(II)

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: [bis(2-methylallyl)cycloocta-1,5-diene]ruthenium(II)
• 英文别名: Ru(η3-2-methylallyl)2(cod)；Ru(π-CH2C(CH3)CH2)2(cod)；Ru(cod)(2-methylallyl)2；(1,5-cyclooctadiene)bismethylallylruthenium；Ru(methallyl)2(COD)；(Ru(1,2:5,6-η-1,5-cyclooctadiene)(η(3)-methallyl)2)；[Ru(2-methylallyl)₂(COD)]；(1,5-cyclooctadiene)Ru(methallyl)2；(COD)Ru[η3-(CH2)2CCH3]2；(COD)(2-methylallyl)2Ru
• 化学式: C₁₆H₂₆Ru
• 分子量: 319.452
• InChiKey: GRYFGFSAXGLJLN-PHFPKPIQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.46
• 重原子数：
  17
• 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：

  [bis(2-methylallyl)cycloocta-1,5-diene]ruthenium(II) 在 氢气 作用下， 以 further solvent(s) 为溶剂， 生成 钌
  参考文献：
  名称：

  Tuning the selectivity of ruthenium nanoscale catalysts with functionalised ionic liquids: Hydrogenation of nitriles

  摘要：

  Ruthenium nanoparticles prepared in nitrile-functionalised ionic liquids (ILs) display unusual selectivities toward the hydrogenation of nitrile containing aromatic compounds. In particular, a selective catalytic hydrogenative coupling of nitriles was observed. In this transformation, nitrile groups are exclusively hydrogenated in the presence of arenes, which are typically hydrogenated by ruthenium nanoparticles in non-functionalised ILs. The catalyst material was characterised by means of TEM and EDS analysis. Furthermore, molecular species formed during the catalytic process were characterised by MS-analysis of the gaseous phase and the ionic liquid phase by ESI/MS Q-TOR. (C) 2009 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2009.08.004
• 作为产物：
  描述：

  dichloro(1,5-cyclooctadiene)ruthenium(II) 、 3-氯-2-甲基丙烯 在 Mg 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以80%的产率得到[bis(2-methylallyl)cycloocta-1,5-diene]ruthenium(II)
  参考文献：
  名称：

  The co-crystallization of Ru((R)-binap)(η3-Me-allyl)2 and binap dioxide, and synthesis of Ru(Ph2P(CH2)4PPh2)(η3-Me-allyl)2

  摘要：

  The molecular structure of the 2-methylallyl species Ru((R)-binap)(eta(3)-Me-allyl)(2) (3) was established by X-ray crystallography of a crystal of 3a, the asymmetric unit of which is composed of half of a molecule of 3 and half of a (R)-(+)-2,2'-bis(-diphenylphosphinoyl)-1,1'-binaphthyl(binap dioxide) molecule, co-crystallized with two disordered deuterobenzenes; crystals of 3a are tetragonal, space group I422, with Z = 8, a = 21.344(1) Angstrom and c = 36.453(2) A. The structure was solved by direct methods and refined by full-matrix least-squares procedures to R = 0.034 and R-w = 0.032 for 3431 reflections with I greater than or equal to 3 sigma(I). The 1,4-bis(diphenylphosphino)butane (dppb) analogue (2) of 3 was also prepared and characterized by H-1 and P-31{H-1}-NMR spectroscopy and elemental analysis, and the reactivities of 2 and 3 toward halogen acids are discussed. (C) 1998 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(97)00758-4
• 作为试剂：
  描述：

  1-苯基-2-吡咯烷酮 在 [bis(2-methylallyl)cycloocta-1,5-diene]ruthenium(II) 、 甲酸 、 双三氟甲烷磺酰亚胺 、 三乙胺 、 1,1,1-三(二苯基膦甲基)乙烷 作用下， 以 二丁醚 为溶剂， 反应 24.0h， 以75%的产率得到1-苯基吡咯烷
  参考文献：
  名称：

  甲酸/三乙胺的Ru催化酰胺酰胺的脱氧转移加氢

  摘要：

  首次报道了使用HCO 2 H / NEt 3作为还原剂的钌（II）催化的酰胺脱氧转移胺成胺。催化剂体系由[Ru（2-甲基烯丙基）2（COD）]，1,1,1-三（二苯基膦甲基）乙烷（triphos）和双（三氟甲烷磺酰亚胺）（HNTf 2）在将各种仲酰胺和叔酰胺脱氧还原成相应的胺方面表现出色，选择性极好，并且对包括还原敏感基团在内的官能团表现出很高的耐受性。氢源和酸助催化剂的选择对于催化至关重要。机理研究表明，通过借入氢对原位生成的醇和胺进行还原胺化是主要途径。

  DOI：

  10.1002/adsc.201900406

文献信息

• Mononuclear ruthenium complex and organic synthesis reaction using same
  申请人：KYUSHU UNIVERSITY, NATIONAL UNIVERSITY CORPORATION

  公开号：US09884316B2

  公开（公告）日：2018-02-06

  A neutral or cationic mononuclear ruthenium divalent complex represented by formula (1) can actualize exceptional catalytic activity in at least one reaction among a hydrosilylation reaction, hydrogenation reaction, and carbonyl compound reduction reaction. (In the formula, R1-R6 each independently represent a hydrogen atom or an alkyl group, aryl group, aralkyl group, organooxy group, monoorganoamino group, diorganoamino group, monoorganophosphino group, diorganophosphino group, monoorganosilyl group, diorganosilyl group, triorganosilyl group, or organothio group optionally substituted by X; at least one pair comprising any of R1-R3 and any of R4-R6 together represents a crosslinkable substituent; X represents a halogen atom, organooxy group, monoorganoamino group, diorganoamino group, or organothio group; L each independently represent a two-electron ligand other than CO and thiourea ligands; two L may bond to each other; and m represents an integer of 3 or 4.)

  根据公式（1）表示的中性或阳离子单核钌二价配合物，可以在至少一个反应中实现卓越的催化活性，包括氢硅化反应、氢化反应和羰基化合物还原反应。 （在公式中，R1-R6每个独立地代表一个氢原子或一个烷基、芳基、芳烷基、有机氧基、单有机胺基、双有机胺基、单有机膦基、双有机膦基、单有机硅基、双有机硅基、三有机硅基或有机硫基，可由X取代；R1-R3和R4-R6中的至少一对共同代表一个可交联的取代基；X代表一个卤素原子、有机氧基、单有机胺基、双有机胺基或有机硫基；L各自独立地代表一个除CO和硫脲配体以外的双电子配体；两个L可以相互结合；m代表一个3或4的整数。）
• Selective Ruthenium-Catalyzed Transformation of Carbon Dioxide: An Alternative Approach toward Formaldehyde
  作者：Max Siebert、Max Seibicke、Alexander F. Siegle、Sabrina Kräh、Oliver Trapp

  DOI：10.1021/jacs.8b10233

  日期：2019.1.9

  one-step synthesis of a formaldehyde derivative starting from carbon dioxide and hydrogen gas utilizing a homogeneous ruthenium catalyst. Here, formaldehyde is obtained as dimethoxymethane, its dimethyl acetal, by selective reduction of carbon dioxide at moderate temperatures (90 °C) and partial pressures (90 bar H2/20 bar CO2) in the presence of methanol. Besides the desired product, only methyl formate

  甲醛是许多工业过程的重要前体，每年在能量不利和原子效率低的工业过程中通过甲醇催化氧化产生数百万吨的规模。在这项工作中，我们提出了一种使用均相钌催化剂从二氧化碳和氢气开始的甲醛衍生物的高选择性一步合成。在这里，甲醛是通过在中等温度 (90 °C) 和分压 (90 bar H2/20 bar CO2) 下在甲醇存在下选择性还原二氧化碳而获得的二甲氧基甲烷，即其二甲基缩醛。除了所需的产物外，仅形成甲酸甲酯，可在连续的催化步骤中将其转化为二甲氧基甲烷。通过对催化体系的综合筛选，
• Disilaruthena- and Ferracyclic Complexes Containing Isocyanide Ligands as Effective Catalysts for Hydrogenation of Unfunctionalized Sterically Hindered Alkenes
  作者：Yusuke Sunada、Hajime Ogushi、Taiji Yamamoto、Shoko Uto、Mina Sawano、Atsushi Tahara、Hiromasa Tanaka、Yoshihito Shiota、Kazunari Yoshizawa、Hideo Nagashima

  DOI：10.1021/jacs.8b00812

  日期：2018.3.21

  Disilaferra- and disilaruthenacyclic complexes containing mesityl isocyanide as a ligand, 3' and 4', were synthesized and characterized by spectroscopy and crystallography. Both 3' and 4' showed excellent catalytic activity for the hydrogenation of alkenes. Compared with iron and ruthenium carbonyl analogues, 1' and 2', the isocyanide complexes 3' and 4' were more robust under the hydrogenation conditions

  合成了含有异氰基异氰化物作为配体 3' 和 4' 的二硅铁和二硅油环配合物，并通过光谱学和晶体学表征。3' 和 4' 对烯烃的加氢均表现出优异的催化活性。与铁和钌的羰基类似物 1' 和 2' 相比，异氰化物配合物 3' 和 4' 在氢化条件下更加坚固，并且即使在较高的温度（~80 °C）和高氢气压力（~ 20 个大气压）。在目前报道的铁催化剂中，铁配合物 3' 对单、二、三和四取代烯烃的氢化表现出最高的催化活性。钌配合物 4' 在非常温和的条件下催化氢化，例如室温和 1 个大气压的 H2。4' 对未官能化的四取代烯烃的加氢具有非常高的催化活性，这一点尤其值得注意，因为它与 Crabtree 和 Pfaltz 报道的铱配合物的活性相当，后者是文献中活性最高的催化剂。DFT 计算表明有两个可能的催化循环，这两个循环都涉及通过晚期过渡金属的 σ 键复分解（氧化氢迁移）由金属-硅键辅助的 H2 活
• Synthesis and characterisation of ruthenium dihydrogen complexes and their reactivity towards B–H bonds
  作者：Jong-Hoo Choi、Nils E. Schloerer、Josefine Berger、Martin H. G. Prechtl

  DOI：10.1039/c3dt52037d

  日期：——

  In this paper the synthesis and characterisation of ruthenium dihydrogen complexes bearing rigid aliphatic PNP pincer-type ligands are described. As one result hydride complexes were synthesised in good to high yields by a one-pot direct hydrogenation reaction. As another finding the dihydrogen complex, stabilised with a N–Me group in the ligand frame, can be converted with dimethylamine borane into

  本文描述了带有刚性脂肪族PNP钳型配体的钌二氢配合物的合成和表征。结果，通过一锅法直接氢化反应以良好至高产率合成了氢化物配合物。另一个发现是，在配体框架中用N–Me基团稳定的二氢配合物可以与二甲胺硼烷一起转化为具有快速B–N的稀有σ-硼配合物[RuH 2（BH 3）（Me-PNP）]。去耦。此外，我们介绍了通过液体注入场解吸/电离技术（LIFDI-MS）对合成的σ复合物进行的首次质谱分析。
• Use of Silylated Formiates as Hydrosilane Equivalents
  申请人：Commissariat a l'Energie Atomique et aux Energies Alternatives

  公开号：US20210292345A1

  公开（公告）日：2021-09-23

  The present invention relates to a method for preparing organic compounds of formula (I) by reaction between a silylated formiate of formula (II) and an organic compound in the presence of a catalyst and optionally of an additive. The invention also relates to use of the method for preparing organic compounds of formula (I) for the preparation of reagents for fine chemistry and for heavy chemistry, as well as in the production of vitamins, pharmaceutical products, adhesives, acrylic fibres, synthetic leathers, and pesticides.

  本发明涉及一种通过在催化剂和可选添加剂的存在下，使式(I)的有机化合物与式(II)的硅烷基甲酸酯之间发生反应来制备有机化合物的方法。 该发明还涉及利用该方法制备式(I)的有机化合物，用于制备精细化学和重化学的试剂，以及在维生素、药品、粘合剂、丙烯酸纤维、合成皮革和杀虫剂的生产中的用途。