[(Rh(μ-SBu(t))(CNBu(t))2)2] | 185222-98-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: [(Rh(μ-SBu(t))(CNBu(t))2)2]
• CAS: 185222-98-4
• 化学式: C₂₈H₅₄N₄Rh₂S₂
• 分子量: 716.707
• InChiKey: OQUQDTFARLAIBP-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.62
• 重原子数：
  36.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  49.44
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  二氯甲烷 、 [(Rh(μ-SBu(t))(CNBu(t))2)2] 以 二氯甲烷 为溶剂， 以81%的产率得到[(Rh(μ-SBut)(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-SBu(t))(1,5-cyclooctadiene))2] 以 乙醚 为溶剂， 以80%的产率得到[(Rh(μ-SBu(t))(CNBu(t))2)2]
  参考文献：
  名称：

  异氰配体诱导的Dirhodium和Diiridium配合物的金属碱度。碘化物与双核配合物的氧化加成反应模型

  摘要：

  [{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

  DOI：

  10.1021/om9605847