[(Rh(μ-Me2Pz)(CNBut)2)2] | 177499-20-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: [(Rh(μ-Me2Pz)(CNBut)2)2]
• 英文别名: [Rh(μ-3,5-dimethylpyrazolate)(CNtBu)2]2
• CAS: 177499-20-6
• 化学式: C₃₀H₅₀N₈Rh₂
• 分子量: 728.592
• InChiKey: QEMIFDBERNBMKZ-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

• 作为反应物：
  描述：

  二氯甲烷 、 [(Rh(μ-Me2Pz)(CNBut)2)2] 以 二氯甲烷 为溶剂， 以70%的产率得到[(Rh(μ-Me2Pz)(Cl)(CNBut)2)2(μ-CH2)]
  参考文献：
  名称：

  Bimetallic Reactivity of Dirhodium Compounds Leading to Functionalized Methylene-Bridged Compounds

  摘要：

  Reactions of [{Rh(mu -Pz)(CNBut)(2)}(2)] (Pz = pyrazolate, 1) with dichloromethane, alpha,alpha -dichlorotoluene, 1,1-dichloroacetone, and methyldichloroacetate gave the functionalized methylene-bridged compounds [{Rh(mu -Pz)(Cl)(CNBut)(2)}(2)(mu -CHR)] (R = H, Ph, COMe, CO2Me), respectively. The molecular structure of [{Rh(mu -Pz)(Cl)(CNBut)(2)}(2){mu -CH(CO2Me)}] was determined by an X-ray diffraction study. Similarly, the thiolate complex [{Rh(mu -SBut)(CNBut)(2)}(3)] was reacted with dichloromethane to give [{Rh(mu -SBut)(Cl)(CNBut)(2)}(2)(mu -CH2)]. The gem-dichloroalkanes are formally broken in three fragments that become a methylene-bridging group and two terminal chloride ligands in these two-center four-electron oxidative-addition reactions. Decreasing the nucleophilicity of the metals via steric effects, while keeping the basicity of the metals constant, leads to a different type of product, as shown by reaction of dichloromethane with [{Rh(mu -Me(2)Pz)(CNBut)(2)}(2)] to give [{Rh(mu -Me(2)Pz)(Cl)(CNBut)(2)}(2)]. A deeper insight into these reactions is provided by reactions of the complex [(cod)Rh(mu -Pz)(2)Rh(CNBut)(2)] with methyl dichloroacetate and dichloromethane to give the mixed-valence Rh(I)-Rh(III) complex [(cod)Rh(mu -Pz)(2)Rh(Cl){eta (1)-CHCl(CO2Me)}(CNBut)(2)] and the methylene-bridged complex [(cod)(Cl)Rh(mu -Pz)(2)(mu -CH2)Rh(Cl)(CNBut)(2)], respectively. The former evidences that the above rections take place in two steps and that the second step involves an internal oxidative-addition reaction following an S(N)2 mechanism. The latter reaction is very suggestive of how cooperative effects can act in a dinuclear complex to induce an unusual reactivity.

  DOI：

  10.1021/om000946h
• 作为产物：
  描述：

  异氰酸叔丁酯 、 [Rh(μ-3,5-dimethylpyrazolate)(C2H4)2]2 以 乙醚 为溶剂， 以77%的产率得到[(Rh(μ-Me2Pz)(CNBut)2)2]
  参考文献：
  名称：

  双核双（γ-吡唑并合）铑（I）配合物的动力学行为，再分布反应和金属间距离

  摘要：

  络合物[{Rh（μ-RPz）（C 2 H 4）2 } 2 ]中的烯烃取代（RPz =吡唑酸酯（Pz）（1），3-甲基吡唑酸酯（MePz）（2），3,5- dimethylpyrazolate（ME 2 PZ）（3）），由叔丁基胩给出[{的Rh（μ-RPZ）（CNBu吨）2 } 2 ]（4，5，6分别地）。配合物4也可以由[{Rh（μ-Pz）（cod）} 2 ]（cod = 1,5-环辛二烯）（7）制备，从而导致4，7，和中间[（COD）的Rh（μ-PZ）2的Rh（CNBu吨）2 ]（8），它也已隔离。对该表观配体再分布反应进行动力学研究，结果为8，表明它遵循二级速率，给出了活化参数ΔH ≠ = 21.8 kcal·mol - 1，ΔS ≠ = -7.4 eu和ΔG ≠ 298 = 24.0 kcal·mol - 1，表明双核络合物是活性物质，似乎没有碎裂发生。配合物的分子结构3，4，8，和[{的Rh（μ-PZ）（CO）2

  DOI：

  10.1021/om960005y