| 1393719-11-3

• CAS: 1393719-11-3
• 化学式: C₉H₂₄B₉Rh
• 分子量: 332.494
• InChiKey: ALMRBSLVTLTILL-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  [(η²-cyclooctene)(η⁴-2-methylbuta-1,3-diene)Rh(μ-Cl)]₂ 、 以 苯 为溶剂， 生成 [3-{(1-3-η³)-1,1-dimethylallyl}-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.