bis(phenyl)dirhodium(III) caprolactamate | 935529-74-1

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: bis(phenyl)dirhodium(III) caprolactamate
• 英文别名: bis-(σ-phenyl)-tetrakis-μ-(caprolactamato)dirhodium(III)；PhRh(cap)4RhPh；benzene;rhodium(3+);3,4,5,6-tetrahydro-2H-azepin-7-olate
• CAS: 935529-74-1
• 化学式: C₃₆H₅₀N₄O₄Rh₂
• 分子量: 808.628
• InChiKey: UPMCUIAZHFZSSD-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  4.25
• 重原子数：
  46
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  142
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为产物：
  描述：

  苯基硼酸1,3-丙二醇酯 、 dirhodium(II) caprolactamate bis(acetonitrile) 在 copper(I) trifluoromethanesulfonate benzene sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 以18%的产率得到bis(phenyl)dirhodium(III) caprolactamate
  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。
• Removal of Metal−Metal Bonding in a Dimetallic Paddlewheel Complex: Molecular and Electronic Structure of Bis(phenyl) Dirhodium(III) Carboxamidate Compounds
  作者：Joffrey Wolf、Rinaldo Poli、Jian-Hua Xie、Jason Nichols、Bin Xi、Peter Zavalij、Michael P. Doyle

  DOI：10.1021/om800631b

  日期：2008.11.24

  tetracarboxamidatodirhodium(III) are reported, and their electronic structures are mapped through XPS, electrochemical, and computational methods. Comparison with the structures of dirhodium(II,II) and dirhodium(II,III) oxidative precursors portrays the diphenyl dirhodium(III) compounds as two square-pyramidal rhodium units that have undergone conrotatory motion in order to optimize metal−ligand bonding. Axial

  报道了双（苯基）四甲酰胺基二ho（III）的独特结构特征和化学稳定性，并通过XPS，电化学和计算方法绘制了它们的电子结构图。与dirhodium（II，II）和dirhodium（II，III）氧化前体的结构比较，将二苯基dirhodium（III）化合物描绘为经历了旋转运动以优化金属-配体键合的两个方形金字塔形铑单元。轴向苯基配体严重偏离了其预期的Rh-Rh-C线性阵列。该系列吡啶鎓化合物的XPS数据与二苯基吡啶鎓（III）化合物不存在铑-铑键一致，并且电化学测量显示单个可逆Rh 2 6+ / Rh 27+氧化还原对。值得注意的是，它们表现出高的热稳定性，并且在苯的形成之前先去除氨基甲酸酯配体的布朗斯台德酸。通过对双-σ-（苯基）-四-μ- （羧酰胺基）dir（III）的电子结构的理论分析来解释苯基赋予铑（III）化合物非同寻常的稳定性的能力，并进行了比较。与先前报道的二亚硝酰二铑（II
• Bis(phenyl)dirhodium(III) Caprolactamate:  A Dinuclear Paddlewheel Complex with No Metal−Metal Bond
  作者：Jason M. Nichols、Joffrey Wolf、Peter Zavalij、Bindhu Varughese、Michael P. Doyle

  DOI：10.1021/ja070122s

  日期：2007.3.1

  The first unambiguous characterization of a stable dirhodium(III) paddlewheel complex 1 is reported. Complex 1 is prepared via the copper-catalyzed aerobic oxidation of 2 in 77% isolated yield. Comparison of the X-ray crystal structure, visible, and X-ray photoelectron spectroscopy of 1, 2, and 3 indicate a cleavage of the Rh-Rh bond in 1. The oxidation of 2 to 1 is proposed to occur through the intermediacy of 3 with the Cu(II)/Cu(I) couple with oxygen as a terminal oxidant and NaBPh4 as a phenyl transfer agent.