| 367276-86-6

• CAS: 367276-86-6
• 化学式: C₃₆H₅₅BN₈O₂Pd
• 分子量: 749.116
• InChiKey: YRFQWBHVULDFPJ-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：

  、 氰乙酸甲酯 生成
  参考文献：
  名称：

  N/O- and C-Bound (Enolato)palladium Complexes with Hydrotris(pyrazolyl)borato Ligands (Tp^R:  R = iPr₂, Me₂) Obtained via Dehydrative Condensation between the Hydroxo Complexes Tp^RPd(Py)OH and Active Methylene Compounds:  Factors Determining the Isomer Distribution and Dimerization of Cyano Compounds

  摘要：

  Reaction of a hydroxopalladium. complex bearing the Tp(iPr2) ligand, (Tp(iPr2))(py)Pd-OH (1(iPr2)), with active methylene compounds, X-CH2-Y 2 [dicyanomethane (2a), methyl cyanoacetate (2b), benzoylacetonitrile (2c)], resulted in dehydrative condensation to afford the N/O-bound enolates, (Tp(iPr2))(py)Pd-X-CH-Y 3(iPr2)a-c. When the hydroxo complex 1(Me2) with the less bulky Tp(Me2) ligand was allowed to react with 2 at 0 degreesC, similar N/O-bound enolato complexes, (Tp(Me2))(py)Pd-X-CH-Y (3(Me2)a-c), were obtained as kinetic products, which were gradually converted to the more stable C-bound enolato complexes (Tp(Me2))(py)Pd-CHXY (4(Me2)a-c) upon warming to 50 degreesC. X-ray crystallography of the N/O- and C-bound enolates reveals that (1) the Pd center adopts the square-planar or square-pyramidal geometry, (2) the structure of the C-bound isomer is consistent with the canonical structure with the localized bonding scheme, and (3) in the N/O-bound isomers the negative charge is delocalized over the X-CH-Y linkage to form the zwitterionic structure. The N-bound enolato complexes 3a,b obtained from cyano compounds further reacted with the cyano compounds to give the 1:2 condensates: i.e., the 2-cyanoethenylamido complexes (Tp(R))(py)Pd-NH-C(CH2Y)=CCN(Y) (6), whereas the C-bound enolates 4(Me2)a,b showed no indication of the dimerization. Thus, the present study reveals that the reactivity of transition-metal enolates is dependent on their structures.

  DOI：

  10.1021/om010448o
• 作为产物：
  描述：

  (κ2-Tp(iPr2))(py)Pd-OH 、 氰乙酸甲酯 在 Na₂SO₄ 作用下， 以 二氯甲烷 为溶剂， 以64%的产率得到
  参考文献：
  名称：

  N/O- and C-Bound (Enolato)palladium Complexes with Hydrotris(pyrazolyl)borato Ligands (Tp^R:  R = iPr₂, Me₂) Obtained via Dehydrative Condensation between the Hydroxo Complexes Tp^RPd(Py)OH and Active Methylene Compounds:  Factors Determining the Isomer Distribution and Dimerization of Cyano Compounds

  摘要：

  Reaction of a hydroxopalladium. complex bearing the Tp(iPr2) ligand, (Tp(iPr2))(py)Pd-OH (1(iPr2)), with active methylene compounds, X-CH2-Y 2 [dicyanomethane (2a), methyl cyanoacetate (2b), benzoylacetonitrile (2c)], resulted in dehydrative condensation to afford the N/O-bound enolates, (Tp(iPr2))(py)Pd-X-CH-Y 3(iPr2)a-c. When the hydroxo complex 1(Me2) with the less bulky Tp(Me2) ligand was allowed to react with 2 at 0 degreesC, similar N/O-bound enolato complexes, (Tp(Me2))(py)Pd-X-CH-Y (3(Me2)a-c), were obtained as kinetic products, which were gradually converted to the more stable C-bound enolato complexes (Tp(Me2))(py)Pd-CHXY (4(Me2)a-c) upon warming to 50 degreesC. X-ray crystallography of the N/O- and C-bound enolates reveals that (1) the Pd center adopts the square-planar or square-pyramidal geometry, (2) the structure of the C-bound isomer is consistent with the canonical structure with the localized bonding scheme, and (3) in the N/O-bound isomers the negative charge is delocalized over the X-CH-Y linkage to form the zwitterionic structure. The N-bound enolato complexes 3a,b obtained from cyano compounds further reacted with the cyano compounds to give the 1:2 condensates: i.e., the 2-cyanoethenylamido complexes (Tp(R))(py)Pd-NH-C(CH2Y)=CCN(Y) (6), whereas the C-bound enolates 4(Me2)a,b showed no indication of the dimerization. Thus, the present study reveals that the reactivity of transition-metal enolates is dependent on their structures.

  DOI：

  10.1021/om010448o