bis-(σ-(4-methoxycarbonylphenyl))-tetrakis-μ-(caprolactamato)dirhodium(III) | 1158952-15-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: bis-(σ-(4-methoxycarbonylphenyl))-tetrakis-μ-(caprolactamato)dirhodium(III)
• 英文别名: 4-MeOOCC6H4Rh(cap)4RhC6H4COOMe-4；methyl benzoate;rhodium(3+);3,4,5,6-tetrahydro-2H-azepin-7-olate
• CAS: 1158952-15-8
• 化学式: C₄₀H₅₄N₄O₈Rh₂
• 分子量: 924.702
• InChiKey: RYMHYCBLUVWZGN-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  3.82
• 重原子数：
  54
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  194
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为产物：
  描述：

  tetrakis(μ-caprolactamato)dirhodium(Rh-Rh) 、 4-甲氧羰基苯硼酸 在 copper(ll) sulfate pentahydrate sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 以97%的产率得到bis-(σ-(4-methoxycarbonylphenyl))-tetrakis-μ-(caprolactamato)dirhodium(III)
  参考文献：
  名称：

  Synthesis of bis(σ-aryl)dirhodium(iii) caprolactamates by oxidative arylation with arylboronic acids

  摘要：

  最近发现的稳定的双(Ï-苯基)己内酰胺二钠盐（III）及其取代衍生物可通过铜催化工艺，以己内酰胺二钠盐和市售芳基硼酸为原料，方便地制备出高产率的产品。

  DOI：

  10.1039/b806283h

文献信息

• Hetero-bis(σ-aryl)dirhodium(III) caprolactamates. Electronic communication between aryl groups through dirhodium(III)
  作者：Jian-Hua Xie、Lei Zhou、Conrad Lubek、Michael P. Doyle

  DOI：10.1039/b821592h

  日期：——

  Fourteen hetero-bis(σ-aryl)dirhodium(III) caprolactamates that differ by the two aryl groups at the axial positions of dirhodium have been synthesized in good yield and characterized. Copper(II) catalyzed oxidation of dirhodium(II) caprolactamate at room temperature in the presence of two arylboronic acids results in a mixture of a hetero-bis(σ-aryl)dirhodium(III) caprolactamate and two homo-bis(σ-aryl)dirhodium(III) caprolactamates for each arylboronic acid combination. The UV-visλmax values for hetero-bisaryldirhodium(III) caprolactamates fall in between those for the corresponding homo-bisaryldirhodium(III) caprolactamates; electronic interaction between the two aryl groups occurs through dirhodium, but this transmission is probably indirect through the caprolactamate ligands rather than directly between rhodiums. The chemical shift for the carbon bound to Rh shows very limited dependence on the substituent from the aryl group on the adjacent Rh. Bisaryldirhodium(III) caprolactamates with electron-withdrawing substitutions have higher oxidation potentials than those with electron-donating substitutions. A plot of oxidation potentials versus the corresponding UV-visible absorption maxima for the bisaryldirhodium(III) caprolactamates shows a relationship between oxidation potentials and λmax values. The electronic/electrochemical information obtained for hetero-bis(σ-aryl)dirhodium(III) caprolactamates suggests that communication between aryl substituents occurs.

  我们以良好的收率合成了 14 种杂环双(Ï-芳基)二氢铑(III)己内酰胺酸盐，它们的不同之处在于二氢铑轴向位置上的两个芳基。在室温下，铜（II）在两个芳基硼酸的存在下催化氧化己内酰胺酸二(II)，结果产生了一种杂双(Ï-芳基)己内酰胺酸二(III)的混合物，每个芳基硼酸组合产生两种同双(Ï-芳基)己内酰胺酸二(III)。杂双芳基己内酰胺钠(III)的紫外-可见δ "最大值介于相应的均双芳基己内酰胺钠(III)的紫外-可见δ "最大值之间；两个芳基之间的电子相互作用是通过二铑进行的，但这种传递可能是通过己内酰胺配体间接进行的，而不是直接在铑之间进行的。与铑结合的碳的化学位移对相邻铑上芳基的取代基的依赖性非常有限。具有抽电子取代的己内酰胺双芳烷基铑(III)的氧化电位高于具有电子捐赠取代的己内酰胺双芳烷基铑(III)。双芳基二氢铑(III)己内酰胺盐的氧化电位与相应的紫外-可见吸收最大值之间的关系曲线图显示了氧化电位与δ "max 值之间的关系。从杂双(Ï-芳基)二氢铑(III)己内酰胺酸盐获得的电子/电化学信息表明，芳基取代基之间存在沟通。