[3-{(1-3-η³)-1,1,2-trimethylallyl}-1,2-(CH₃)₂-3,1,2-closo-RhC₂B₉H₉] | 1393719-15-7

• 英文名称: [3-{(1-3-η³)-1,1,2-trimethylallyl}-1,2-(CH₃)₂-3,1,2-closo-RhC₂B₉H₉]
• 英文别名: [3-{(1-3-η3)-C6H11}-1,2-Me2-closo-3,1,2-RhC2B9H9]
• CAS: 1393719-15-7
• 化学式: C₁₀H₂₆B₉Rh
• 分子量: 346.521
• InChiKey: YLRJYJLMUCXIMK-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  [3-{(1-3-η³)-1,1,2-trimethylallyl}-1,2-(CH₃)₂-3,1,2-closo-RhC₂B₉H₉] 在 1,8-双二甲氨基萘 作用下， 以 甲苯 为溶剂， 反应 12.0h， 以49%的产率得到
  参考文献：
  名称：

  Base-mediated transformation of the agostic (π-allyl)-closo-rhodacarboranes into complexes with an open (1-5-η5)-pentadienyl ligand

  摘要：

  在冷却（+5°C）的甲苯溶液中，agostic（CH3≡Rh）配合物[3-{(1-3-Μ3)-1,1,2-三甲基烯丙基}-1-R-2-R²-闭-3,1,2-RhC2B9H9] [1: R = R² = Me；2: R,R² = Μ-(邻-二甲苯基)；3: R = Ph, R² = Me]与强非亲核碱N,N,N²,N²-四甲基萘-1,8-二胺（tmnd）的反应，正式涉及将一个配合物分子的Β-烯丙基配体与第二个配合物分子的Β-烯丙基配体进行线性偶联，最终形成结构新颖的单核物种[3-{(1-5-Μ5)-2,3-二甲基-5-(3-甲基丁烯-2-基)戊二烯基}-1-R-2-R²-闭-3,1,2-RhC2B9H9] (4, 5)和(6a,b，非对映异构体的混合物)。配合物5和6a,b也可以使用较弱的碱（如PPh3或甚至EtOH）代替tmnd制备。所有新的配合物

  DOI：

  10.1039/c3dt52838c
• 作为产物：
  描述：

  [(η²-cyclooctene)(η⁴-2,3-dimethylbuta-1,3-diene)Rh(μ-Cl)]₂ 、 以 苯 为溶剂， 生成 [3-{(1-3-η³)-1,1,2-trimethylallyl}-1,2-(CH₃)₂-3,1,2-closo-RhC₂B₉H₉]
  参考文献：
  名称：

  Mixed-ligand di-µ-chloro-bridged Rhodium Dimers as Key Intermediates in the Synthesis of Acyclic (p-allyl)-closo-rhodacarboranes

  摘要：

  The mixed-ligand di-mu-chloro-bridged rhodium dimers [(eta(2)-C8H14)(eta(4)-2-methylbuta-1,3-diene)Rh(mu-Cl)](2) and [eta(2)-C8H14)(eta(4)-2,3-dimethylbuta-1,3-diene)Rh(mu-Cl)](2) were synthesized and characterized. These compounds are key precursors in the preparative synthesis of the acyclic (pi-allyl)-closo-rhodacarborane complexes [3- (pi-(R ''-allyl)}-1-R-2-R'-closo-3,1,2-RhC2B9H9], which were obtained earlier via the one-pot metallation of the K+ salts of the [7-R-8-R'-nido-7,8-C2B9H10](-) anions with [(eta(2)-C8H14)(4)Rh-2(mu-Cl)(2)] in the presence of substituted buta-1,3-diene ligands.

  DOI：

  10.1016/j.mencom.2013.07.004

文献信息

• New Acyclic (π-Allyl)<i>-closo</i>-rhodacarboranes with an Agostic CH₃···Rh Bonding Interaction That Operate as Unmodified Rhodium-Based Catalysts for Alkene Hydroformylation
  作者：Konstantin I. Galkin、Sergey E. Lubimov、Ivan A. Godovikov、Fedor M. Dolgushin、Alexander F. Smol’yakov、Elena A. Sergeeva、Vadim A. Davankov、Igor T. Chizhevsky

  DOI：10.1021/om300432j

  日期：2012.9.10

  A series of new agostic (CH3 center dot center dot center dot Rh) (pi-allyl)-closo-rhodacarboranes (pi-allyl = 1,1-dimethylallyl, 1,2-dimethylallyl, 1,1,2-trimethylallyl, 1,2,3-trimethylallyl), stable in the solid state, have been synthesized via one-pot reactions between the K+ salts of the [7-R-8-R'-7,8-nido-C2B9H10](-) monoanions (1a, R = R' = Me; 1b, R,R' = p-(o-xylylene); 1c, R,R' = p-(CH2)(3)) and the di-mu-chloro cyclooctene rhodium dimer [(eta(2)-C8H14)(4)Rh-2(mu-Cl)(2)] (2) in the presence of a 3-fold excess of the conjugated 1,3-dienes 2-methylbuta-1,3-diene (isoprene, 3), 2,3-dimethylbuta-1,3-diene (4), and 3-methylpenta-1,3-diene (5). The agostic structures of [3-(1-3-eta(3))-1,1-dimethylallyl}-1,2-(CH3)(2)-3,1,2-closo-RhC2B9H9] (7a) and [3-(1-3-eta(3))-1,1,2-trimethylallyl}-1,2-(CH3)(2)-3,1,2-closo-RhC2B9H9] (8a) have been unambiguously confirmed by single-crystal X-ray diffraction studies. Two of these pi-allyl complexes prepared were evaluated for their efficacy in hydroformylation of the model alkenes under syngas (CO/H-2) using supercritical carbon dioxide (scCO(2)) as the solvent, and both display excellent conversion and high regioselectivity in the formation of aldehyde products.