dicarbonyldi-μ-chloro-cis,cis-η4-1,5-cyclooctadienedirhodium(I) | 49855-72-3

• 英文名称: dicarbonyldi-μ-chloro-cis,cis-η4-1,5-cyclooctadienedirhodium(I)
• CAS: 49855-72-3
• 化学式: C₁₀H₁₂Cl₂O₂Rh₂
• 分子量: 440.921
• InChiKey: RMUVDYHFDUONAO-IVCCQKQOSA-L

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

• 作为反应物：
  描述：

  dicarbonyldi-μ-chloro-cis,cis-η4-1,5-cyclooctadienedirhodium(I) 、 trans-[Ru(pyridine)₄(CN)₂] 以 氯仿 为溶剂， 生成
  参考文献：
  名称：

  Heterometallic cyanide-bridged complexes containing RhIRuIIRhI triad: NMR data on exchange reactions and ligand effect transmission

  摘要：

  Trans-[RuPy4(CN)(2) cleaves chloro-rhodium bridges in rhodium(I) binuclear complexes, [Rh(CO)(2)Cl](2), [Rh(Cod)Cl](2), and [(Cod)RhCl2Rh(CO)(2)] yielding heterometallic triad complexes, [(CO)(2)ClRh(NC)RuPy4(CN)RhCl(CO)(2)] (I), [(Cod)ClRh(NC)RuPy4(CN)RhCl(Cod)] (II), and [(Cod)ClRh(NC)RuPy4(CN)RhCl(CO)(2)] (III), respectively. In solutions, III coexists with equilibrium amounts of I and II in the near-binomial proportions. Under action of [Rh(CO)(2)Cl](2), II transforms into I with parallel formation of [Rh(Cod)Cl](2). Ligand effect transmission along the L-Rh-NC-Ru-CN-Rh-L' chain is studied by H-1 and C-13 NMR. Chemical shifts delta H-1 and delta C-13 of Ru-bound Py ligands are sensitive to the nature of Rh-bound ligands. Values of delta H-1 and delta C-13 of Cod and C-13 of CO ligands are sensitive to the ligands at the remote end of the L-Rh-NC-Ru-CN-RhL' chain. Reaction of trans-[RuPy4(CN)(2)] with Rh-2(OAc)(4) yields an apparently linear polymer [-Rh(OAc)(4)Rh-NCRuPy4CN-]. Upon action of [Rh(CO)(2)Cl](2), the polymer decomposes yielding I and Rh-2(OAc)(4). X-ray structure data for I are given. (C) 2009 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2009.04.028
• 作为产物：
  描述：

  1,5-环辛二烯 、 di(rhodium)tetracarbonyl dichloride 以 正己烷 为溶剂， 以95%的产率得到dicarbonyldi-μ-chloro-cis,cis-η4-1,5-cyclooctadienedirhodium(I)
  参考文献：
  名称：

  Rh 2（CO）4 Cl 2与1,5-环辛二烯和四甲基丙烯烯的反应。原位振动光谱学，光谱重建和DFT研究相结合

  摘要：

  Rh 2（CO）4 Cl 2与1,5-环辛二烯（COD）和四甲基烯丙二烯（TMA）的反应分别在无水己烷和氩气气氛下进行。反应期间还对Rh 2（CO）4 Cl 2，COD和TMA进行了多次扰动。通过原位FTIR（FIR和MIR）和/或拉曼光谱仪监测这两个反应，并使用BTEM系列算法对收集的光谱进行进一步分析。进行DFT计算以鉴定存在的有机金属物质。已知的二烯复杂的Rh 2（CO）2氯2（η 4 -C 8 ħ 12）和新的丙二烯络合物的Rh 2（CO）3氯2（η 2 -C 7 ħ 12）被形成为两个主要有机铑产品。它们的纯组分光谱在200–680、800–1360和1500–2200 cm -1的三个特征区域中重建。它们的相对浓度也通过羰基区域1500-2200cm -1的最小二乘拟合获得。本文稿显示了结合原位光谱测量，BTEM分析和DFT光谱预测的有用性，以分析高稀释度的有机金属反应并鉴定反应产物。

  DOI：

  10.1016/j.jorganchem.2010.07.018

文献信息

• Synthesis and X-ray powder diffraction characterization of (OC)2RhCl2Rh(cod) (cod = cycloocta-1,4-diene)
  作者：Eleonora Corradi、Norberto Masciocchi、Gyula Pályi、Renato Ugo、Anna Vizi-Orosz、Claudia Zucchi、Angelo Sironi

  DOI：10.1039/a704668e

  日期：——

  In order to elucidate the nature and the structure of the elusive (OC)2Rh(Ph3SiO)2Rh(cod) (cod) = cycloocta-1,5-diene) complex, an important model compound for surface catalysis, (OC)2RhCl2Rh(cod) has been synthesized, and structurally characterized by ab initio X-ray powder diffraction. Crystals of (OC)2RhCl2Rh(cod) are monoclinic, space group P21/c, a = 6.659(1), b = 12.274(1) and c = 16.096(1) Å, β = 92.176(5)°, Z = 4, ρcalc = 2.209 g cm–3. The structure has been solved, from powder diffraction data only, by Patterson and Fourier-difference methods and has been ultimately refined, by the Rietveld method, down to Rp = 0.116 and Rwp = 0.154 for 4050 data points collected in the 12–93° (2θ) range. The molecule contains two square-planar rhodium atoms, one bearing two terminal carbonyls and the other bound to the chelating cod fragment, and two chlorine atoms bridging the Rh· · ·Rh vector. The Rh2Cl2 core is markedly non-planar, the dihedral angle about the Cl· · ·Cl hinge being 135.4(6)°.

  为了阐明难以捉摸的 (OC)2Rh(Ph3SiO)2Rh(cod)（cod = 环辛烷-1,5-二烯）复合物（一种重要的表面催化模型化合物）的性质和结构，我们合成了 (OC)2RhCl2Rh(cod)，并利用 ab initio X 射线粉末衍射对其进行了结构表征。(OC)2RhCl2Rh(cod) 晶体为单斜晶系，空间群为 P21/c，a = 6.659(1)、b = 12.274(1)和 c = 16.096(1)埃，β = 92.176(5)°，Z = 4，ρcalc = 2.209 g cm-3。通过帕特森法和傅里叶差分法，仅从粉末衍射数据中求解出了该结构，并通过里特维尔德法，在 12-93° (2θ) 范围内收集了 4050 个数据点，最终将其细化为 Rp = 0.116 和 Rwp = 0.154。该分子包含两个方形平面铑原子，其中一个带有两个末端羰基，另一个与螯合 cod 片段结合，还有两个氯原子桥接在 Rh- -Rh 向量上。Rh2Cl2 核心明显非平面，与 Cl- -Cl 铰链的二面角为 135.4(6)°。
• Varshavskii, Yu. S.; Cherkasov, T. G.; Bresler, L. S., Koordinatsionnaya Khimiya, 1986, vol. 12, p. 452 - 460
  作者：Varshavskii, Yu. S.、Cherkasov, T. G.、Bresler, L. S.

  DOI：——

  日期：——
• Dicarbonyldi-μ-chloro-<i>cis,cis</i>-η⁴-1,5-cyclooctadienedirhodium(I)
  作者：Maurice Abou Rida、Joseph Saikaili、Anthony K. Smith、Alain Thozet

  DOI：10.1107/s0108270100020035

  日期：2001.4.15

  The title compound, dicarbonyl-1 kappa C-2-di-mu -chloro-1:2 kappa Cl-4-[cis,-cis-2(eta (4))-1,5-cyclooctadiene]dirhodium(I), [Rh2Cl2(C8H12)-(CO)(2)], consists of a dichloro-bridged dimer of rhodium, with a non-bonded Rh . . . Rh distance of 3.284 (2) Angstrom. One Rh atom is coordinated to two carbonyl ligands, while the other Rh atom is coordinated to the cyclooctadiene moiety.