| 1393719-19-1

• CAS: 1393719-19-1
• 化学式: C₁₆H₂₈B₉Rh
• 分子量: 420.603
• InChiKey: AHZWCMDWPOXCLY-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  在 1,8-双二甲氨基萘 作用下， 以 甲苯 为溶剂， 反应 12.0h， 以75%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：

  2,3-二甲基-1,3-丁二烯 、 chlorobis(cyclooctene)rhodium(I) dimer 、 K[7,8-μ-(o-xylylene)-7,8-nido-C₂B₉H₁₀] 以 苯 为溶剂， 反应 1.5h， 以58%的产率得到
  参考文献：
  名称：

  New Acyclic (π-Allyl)-closo-rhodacarboranes with an Agostic CH₃···Rh Bonding Interaction That Operate as Unmodified Rhodium-Based Catalysts for Alkene Hydroformylation

  摘要：

  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.

  DOI：

  10.1021/om300432j