[3-{(1-3-η³)-1,1,2-trimethylallyl}-1,2-μ-(CH₂)₃-3,1,2-closo-RhC₂B₉H₉] | 1393719-20-4

• 英文名称: [3-{(1-3-η³)-1,1,2-trimethylallyl}-1,2-μ-(CH₂)₃-3,1,2-closo-RhC₂B₉H₉]
• CAS: 1393719-20-4
• 化学式: C₁₁H₂₆B₉Rh
• 分子量: 358.532
• InChiKey: AGMJYPQOOKELAJ-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  chlorobis(cyclooctene)rhodium(I) dimer 、 K[7,8-μ-(CH₂)₃-7,8-nido-C₂B₉H₁₀] 、 2,3-二甲基-1,3-丁二烯 以 苯 为溶剂， 反应 3.5h， 以76%的产率得到[3-{(1-3-η³)-1,1,2-trimethylallyl}-1,2-μ-(CH₂)₃-3,1,2-closo-RhC₂B₉H₉]
  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
• 作为试剂：
  描述：

  一氧化碳 、 (S)-(-)-柠檬烯 在 [3-{(1-3-η³)-1,1,2-trimethylallyl}-1,2-μ-(CH₂)₃-3,1,2-closo-RhC₂B₉H₉] 、 氢气 作用下， 以 二氧化碳 为溶剂， 60.0 ℃ 、3.04 MPa 条件下， 反应 5.0h， 生成 C₁₁H₁₈O
  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