[(Rh(μ-pyrazolate)(CNBu(t))2)2] | 143626-50-0

• 英文名称: [(Rh(μ-pyrazolate)(CNBu(t))2)2]
• 英文别名: [Rh(μ-pyrazolate)(CNtBu)2]2；[(Rh(μ-Pz)(CNBut)2)2]
• CAS: 143626-50-0
• 化学式: C₂₆H₄₂N₈Rh₂
• 分子量: 672.484
• InChiKey: LAQZTALFNNPJEN-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：

  [(Rh(μ-pyrazolate)(CNBu(t))2)2] 在 碘甲烷 作用下， 以 乙醚 为溶剂， 生成
  参考文献：
  名称：

  Reactions of chloroform and gem-dichlorocarbons with binuclear rhodium complexes leading to functionalized methylene-bridged compounds

  摘要：

  Chloroform and gem-dichlorocarbons CHCl2R (R = H, Ph or CO2Me) react rapidly with the binuclear basic metal complex [{Rh(mu-pz)(CNBut)2}2] (pz = pyrazolate) under a three-fragment four-electron scheme to give mainly the compounds [{Rh(mu-pz)Cl(CNBut)2}2(mu-CHR)] (R = Cl, H, CO2Me or Ph) and [{Rh(mu-pz)Cl(CNBut)2}2] as a side-product.

  DOI：

  10.1039/dt9920002123
• 作为产物：
  描述：

  [Rh(μ-pyrazolate)(C2H4)2]2 、 异氰酸叔丁酯 以 乙醚 为溶剂， 以95%的产率得到[(Rh(μ-pyrazolate)(CNBu(t))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

文献信息

• New Perspective on the Formation and Reactivity of Metal−Metal-Bonded Dinuclear Rhodium and Iridium Complexes
  作者：Cristina Tejel、Miguel A. Ciriano、José A. López、Fernando J. Lahoz、Luis A. Oro

  DOI：10.1021/om970347j

  日期：1997.10.1

  Reactions of the binuclear complexes [M(μ-Pz)(CNBut)2}2] (M = Rh (1), Ir (2); Pz = pyrazolate) with diiodine give the metal−metal-bonded complexes [M(μ-Pz)(I)(CNBut)2}2] (M = Rh (3), Ir (4)). A further reaction with diiodine afford the complexes [M(μ-Pz)(I)(CNBut)2}2(μ-I)]I, which react cleanly with CF3SO3Me replacing the ionic iodide by the triflate group. The M(I) complexes 1 and 2 are easily oxidized

  双核络合物[M（μ-Pz）（CNBu t）2 } 2 ]（M = Rh（1），Ir（2）; Pz =吡唑酸盐）与二碘的反应产生金属与金属键合的络合物[ M（μ-Pz）（I）（CNBu t）2 } 2 ]（M ＝ Rh（3），Ir（4））。与二碘进一步反应，得到配合物[M（μ-Pz）（I）（CNBu t）2 } 2（μ-I）] I，它与CF 3 SO 3 Me干净地反应，用三氟甲磺酸盐代替离子碘化物团体。M（I）配合物1和2易被中性氧化剂如[Cp 2 Fe] +氧化而得到金属-金属键合的指示剂[M（μ-Pz）（CNBu t）2（MeCN）} 2 ] 2+），这会增加卤离子的产生中性配合物[M（μ-Pz）（X）（CNBu t）2 } 2 ]（M = Rh，X = Cl（7）； M = Rh，Ir，X = I）。这些反应表明金属-金属键的形成具有电子转移特性。[I（Py）2 ] BF的
• Metal Basicity of Dirhodium and Diiridium Complexes Induced by Isocyanide Ligands. Model for the Oxidative-Addition Reaction of Methyl Iodide with Dinuclear Complexes
  作者：Cristina Tejel、Miguel A. Ciriano、Andrew J. Edwards、Fernando J. Lahoz、Luis A. Oro

  DOI：10.1021/om9605847

  日期：1997.1.1

  metal basicity induced by the isocyanide ligands. However, the influence of the nature of the metals is evident in the reactions of the mixed-ligand complexes [(cod)M(μ-Pz)2M(CNBut)2] (M = Rh, Ir; cod = 1,5-cyclooctadiene) with MeI to give the mixed-valence Rh(I)−Rh(III) complex [(cod)Rh(μ-Pz)2Rh(Me)(I)(CNBut)2] and the Ir(III) complex [(cod)(Me)Ir(μ-Pz)2(μ-I)Ir(Me)(CNBut)2]I, respectively. The former

  [Rh（μ-Pz）（CNBu t）2 } 2 ]（1）与新化合物[M（μ-L）（CNBu t）2 } 2 ]（M = Rh，L = SBu t； M = Ir，L =吡唑酸酯（Pz））和MeI给出[Rh（μ-Pz）（Me）（CNBu t）2 } 2（μ-I）] I（2），[Rh（μ- SBu t）（Me）（CNBu t）2 } 2（μ-I）] I和[Ir（μ-Pz）（Me）（CNBu t）2 } 2（μ-I）] I。在每个金属中心发生的氧化加成反应是立体选择性的。由于异氰酸酯配体诱导的强金属碱性，未观察到与金属性质相关的反应性差异。但是，金属的性质的影响在混合配体络合物[（cod）M（μ-Pz）2 M（CNBu t）2 ]（M = Rh，Ir; cod = 1， 5-环辛二烯）与MeI形成混合价Rh（I）-Rh（III）络合物[（cod）Rh（μ-Pz）2 Rh（Me）（I）（CNBu
• Rhodium and Iridium Pyrazolato Blues
  作者：Cristina Tejel、Miguel A. Ciriano、José A. López、Fernando J. Lahoz、Luis A. Oro

  DOI：10.1002/(sici)1521-3773(19980619)37:11<1542::aid-anie1542>3.0.co;2-l

  日期：1998.6.19

  The staggered arrangement of the two dimers in 1 facilitates the formation of an almost linear chain of four metal centers that is held together by a nonsupported metal-metal bond. The intense color of the compounds and the fractional oxidation states of the metal atoms can be explained by electron delocalization along the chain. M=Rh, Ir.
• Bimetallic Reactivity of Dirhodium Compounds Leading to Functionalized Methylene-Bridged Compounds
  作者：Cristina Tejel、Miguel A. Ciriano、Luis A. Oro、Antonio Tiripicchio、Franco Ugozzoli

  DOI：10.1021/om000946h

  日期：2001.4.1

  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.