Rh3Cp3(μ3-CPh)2 | 88801-72-3

• 英文名称: Rh3Cp3(μ3-CPh)2
• CAS: 88801-72-3
• 化学式: C₂₉H₂₅Rh₃
• 分子量: 682.234
• InChiKey: NQQTYNFOLQANRW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  以 neat (no solvent, gas phase) 为溶剂， 以43%的产率得到Rh3Cp3(μ3-CPh)2
  参考文献：
  名称：

  炔烃在三金属框架上的断裂：实验证据和理论分析

  摘要：

  DOI：

  10.1021/om00082a020

文献信息

• Benzylidyne-capped group 9 trinuclear clusters: synthesis, structure and properties of trirhodium and cobalt–rhodium mixed-metal clusters [Co3−Rh Cp3(μ3-CPh)2] (n=1,2,3)
  作者：Masahiro Ebihara、Masami Iiba、Satohisa Higashi、Naoki Tsuzuki、Takashi Kawamura、Tsunenori Morioka、Shinji Ozawa、Tokio Yamabe、Hideki Masuda

  DOI：10.1016/j.poly.2003.09.001

  日期：2003.11

  The benzylidyne-capped trirhodium and cobalt-rhodium mixed-metal clusters [M3Cp3(mu(3)-CPh)(2)] (M-3:Rh-3, 1; CoRh2, 2; Co2Rh, 3) were synthesized. Complex 1 was prepared from [CpRh(CO)(2)] and diphenylacetylene. Complexes 2 and 3 were synthesized by using a mixture of [CpRh(CO)(2)] and [CpCo(CO)(2)] and separated with silica-gel column chromatography. The molecular structures of 1, 2 and 3 were determined. The average Rh-Rh distance (2.617(8) Angstrom) in 2 is nearly equal to that in 1 (2.620(13) Angstrom), and the average Co-Rh distance (2.503(16) Angstrom) in 2 is similar to the average of the average Co-Co (2.382(8) Angstrom) length in [Co3Cp3(mu(3)-CPh)(2)] (4) and the average Rh-Rh distance in 1. Clusters 2, 3 and 4 showed a chemically reversible one-electron oxidation and a chemically reversible one-electron reduction response in MeCN. For 1, a chemically reversible one-electron reduction and irreversible oxidation waves were observed in MeCN, whereas in CH2Cl2, two chemically reversible oxidation waves were observed. The oxidation and the reduction potentials shifted to more positive and more negative potential, respectively, with an increase of the number of rhodium atoms. The anionic radical of 3 was generated by the reaction with potassium metal in 2-methyltetrahydrofuran and was examined with ESR. The isotropic hyperfine coupling constant of the Co-59 nuclei of 3(-) was slightly smaller than that of 4(-). Geometry optimization of model complexes [M3Cp3(mu(3)-CH)(2)] (M-3: Rh-3, 1'; CoRh2, 2'; Co2Rh, 3') was carried out by a density functional theory (DFT) calculation. Assignments of low-energy UV-Vis absorption bands for 1 and 4 are proposed based on transitions of 1' and [Co3Cp3(mu(3)-CH)(2)] (4) calculated by time-dependent DFT. (C) 2003 Elsevier Ltd. All rights reserved.