| 210363-36-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 210363-36-3
• 化学式: C₂₅H₄₅N₂OP₂Rh
• 分子量: 554.498
• InChiKey: BTNJURAIKZJAOM-UHFFFAOYSA-M

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：

  以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  Alkyl− and Aryl−Oxygen Bond Activation in Solution by Rhodium(I), Palladium(II), and Nickel(II). Transition-Metal-Based Selectivity

  摘要：

  Reaction of [RhCl(C8H14)(2)](2) (C8H14 = cyclooctene)with 2 equiv of the aryl methyl ether phosphine 1 in C6D6 results in an unprecedented metal insertion into the strong sp(2)-sp(3) aryl-O bond. This remarkable reaction proceeds even at room temperature and occurs directly, with no intermediacy of C-H activation or insertion into the adjacent weaker ArO-CH3 bond. Two new phenoxy complexes (8 and 9), which are analogous to the product of insertion into the ArO-CH3 bond (had it taken place) were prepared and shown not to be intermediates in the Ar-OCH3 bond cleavage process. Thus, aryl-O bond activation by the nucleophilic Rh(I) is kinetically preferred over activation of the alkyl-O bond. The phenoxy Rh(I)-eta(1)-N-2 complex (8) is in equilibrium with the crystallographically characterized Rh(I)-mu-N-2-Rh(I) dimer (12). Reaction of [RhCl(C8H14)(2)](2) With 2 equiv of the aryl methyl ether phosphine 2, PPh3, and excess HSiR3 (R = OCH2CH3, CH2CH3) results also in selective metal insertion into the aryl-O bond and formation of (CH3O)SiR3. Thus, transfer of a OCH3 group from carbon to silicon was accomplished, showing that hydrosilation of an unstrained aryl-O single bond by a primary silane is possible. The selectivity of C-O bond activation is markedly dependent on the transition-metal complex and the alkyl group involved, allowing direction of the C-O bond activation process at either the aryl-O or alkyl-O bond. Thus, contrary to the reactivity of the rhodium complex, reaction of NiI2 or Pd(CF3CO2)(2) with 1 equiv of 1 in ethanol or C6D6 at elevated temperatures results in exclusive activation of the sp(3)-sp(3) ArO-CH3 bond, while reaction of the analogous aryl ethyl ether 4 and Pd(CF3CO2)(2) results in both sp(3)-sp(3) and sp(2)-sp(3) C-O bond activation. The resulting phenoxy Pd(II) complex (18) is fully characterized by X-ray analysis. Heating the latter under mild dihydrogen pressure results in hydrodeoxygenation to afford an aryl-Pd(II) complex (19).

  DOI：

  10.1021/ja9738889
• 作为产物：
  描述：

  [RhCl(cyclooctene)]₂ 、 氮 、 2,6-Bis[(di-tert-butylphosphanyl)methyl]-4-methylphenol 在 KH 作用下， 以 四氢呋喃 为溶剂， 以>99的产率得到
  参考文献：
  名称：

  Alkyl− and Aryl−Oxygen Bond Activation in Solution by Rhodium(I), Palladium(II), and Nickel(II). Transition-Metal-Based Selectivity

  摘要：

  Reaction of [RhCl(C8H14)(2)](2) (C8H14 = cyclooctene)with 2 equiv of the aryl methyl ether phosphine 1 in C6D6 results in an unprecedented metal insertion into the strong sp(2)-sp(3) aryl-O bond. This remarkable reaction proceeds even at room temperature and occurs directly, with no intermediacy of C-H activation or insertion into the adjacent weaker ArO-CH3 bond. Two new phenoxy complexes (8 and 9), which are analogous to the product of insertion into the ArO-CH3 bond (had it taken place) were prepared and shown not to be intermediates in the Ar-OCH3 bond cleavage process. Thus, aryl-O bond activation by the nucleophilic Rh(I) is kinetically preferred over activation of the alkyl-O bond. The phenoxy Rh(I)-eta(1)-N-2 complex (8) is in equilibrium with the crystallographically characterized Rh(I)-mu-N-2-Rh(I) dimer (12). Reaction of [RhCl(C8H14)(2)](2) With 2 equiv of the aryl methyl ether phosphine 2, PPh3, and excess HSiR3 (R = OCH2CH3, CH2CH3) results also in selective metal insertion into the aryl-O bond and formation of (CH3O)SiR3. Thus, transfer of a OCH3 group from carbon to silicon was accomplished, showing that hydrosilation of an unstrained aryl-O single bond by a primary silane is possible. The selectivity of C-O bond activation is markedly dependent on the transition-metal complex and the alkyl group involved, allowing direction of the C-O bond activation process at either the aryl-O or alkyl-O bond. Thus, contrary to the reactivity of the rhodium complex, reaction of NiI2 or Pd(CF3CO2)(2) with 1 equiv of 1 in ethanol or C6D6 at elevated temperatures results in exclusive activation of the sp(3)-sp(3) ArO-CH3 bond, while reaction of the analogous aryl ethyl ether 4 and Pd(CF3CO2)(2) results in both sp(3)-sp(3) and sp(2)-sp(3) C-O bond activation. The resulting phenoxy Pd(II) complex (18) is fully characterized by X-ray analysis. Heating the latter under mild dihydrogen pressure results in hydrodeoxygenation to afford an aryl-Pd(II) complex (19).

  DOI：

  10.1021/ja9738889