| 131703-22-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 131703-22-5
• 化学式: C₄₈H₅₁ClNP₃RuSi₂
• 分子量: 927.555
• InChiKey: BXUAUTIRGRAMDZ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  10.64
• 重原子数：
  56.0
• 可旋转键数：
  8.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  3.24
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  在 allylmagnesium bromide or MeLi or Me₃SiCH₂Li 作用下， 以 四氢呋喃 为溶剂， 以92%的产率得到
  参考文献：
  名称：

  Synthesis and reactivity of ruthenium amide-phosphine complexes. Facile conversion of a ruthenium amide to a ruthenium amine via dihydrogen activation and orthometalation. X-ray structure of RuCl(C6H4PPh2)[NH(SiMe2CH2PPh2)2]

  摘要：

  The reaction of LiN(SiMe2CH2PPh2)2 with RuCl2(PPh3)3 leads to the formation of the ruthenium amide complex RuCl(PPh3)[N(SiMe2CH2PPh2)2]. This complex reacts with H2 to form two isomeric amine-hydride derivatives of the formula RuCl(PPh3)H[NH(SiMe2CH2PPh2)2]. Reaction of RuCl(PPh3)[N-(SiMe2CH2PPh2)2] with MeLi, Me3SiCH2Li, or H2C = CHCH2MgCl does not lead to the expected hydrocarbyl derivative; rather, ortho metalation occurs to generate Ru(C6H4PPh2)[N(SiMe2CH2PPh2)2]. Attempts to displace the PPh3 ligand of RuCl(PPh3)[N(SiMe2CH2PPh2)2] with PEt3 lead to the formation of RuCl(C6H4PPh2)[NH(SiMe2PPh2)2], having an amine ligand and the ortho-metalated phenyl group. The complex RuCl(C6H4PPh2)[NH(SiMe2CH2PPh2)2] crystallizes in space group P2(1)/n with a = 9.8385 (5) angstrom, b = 29.561 (1) angstrom, c = 20.8665 (9) angstrom, beta = 101.683 (4)-degrees, V = 5942.2 (5) angstrom3, and Z = 4. Transformation of an amide linkage to an amide via H2 activation or ortho metalation is apparently driven by the formation of an intramolecular hydrogen bond between the amine hydrogen and the coordinated chloride; the N-H...Cl distance is 2.76 (6) angstrom, which is shorter than the expected van der Waals separation of 3.0 angstrom.

  DOI：

  10.1021/om00048a025
• 作为产物：
  描述：

  tris(triphenylphosphine)ruthenium(II) chloride 、 lithium;bis[diphenylphosphanylmethyl(dimethyl)silyl]azanide 以 四氢呋喃 为溶剂， 以62%的产率得到
  参考文献：
  名称：

  Synthesis and reactivity of ruthenium amide-phosphine complexes. Facile conversion of a ruthenium amide to a ruthenium amine via dihydrogen activation and orthometalation. X-ray structure of RuCl(C6H4PPh2)[NH(SiMe2CH2PPh2)2]

  摘要：

  The reaction of LiN(SiMe2CH2PPh2)2 with RuCl2(PPh3)3 leads to the formation of the ruthenium amide complex RuCl(PPh3)[N(SiMe2CH2PPh2)2]. This complex reacts with H2 to form two isomeric amine-hydride derivatives of the formula RuCl(PPh3)H[NH(SiMe2CH2PPh2)2]. Reaction of RuCl(PPh3)[N-(SiMe2CH2PPh2)2] with MeLi, Me3SiCH2Li, or H2C = CHCH2MgCl does not lead to the expected hydrocarbyl derivative; rather, ortho metalation occurs to generate Ru(C6H4PPh2)[N(SiMe2CH2PPh2)2]. Attempts to displace the PPh3 ligand of RuCl(PPh3)[N(SiMe2CH2PPh2)2] with PEt3 lead to the formation of RuCl(C6H4PPh2)[NH(SiMe2PPh2)2], having an amine ligand and the ortho-metalated phenyl group. The complex RuCl(C6H4PPh2)[NH(SiMe2CH2PPh2)2] crystallizes in space group P2(1)/n with a = 9.8385 (5) angstrom, b = 29.561 (1) angstrom, c = 20.8665 (9) angstrom, beta = 101.683 (4)-degrees, V = 5942.2 (5) angstrom3, and Z = 4. Transformation of an amide linkage to an amide via H2 activation or ortho metalation is apparently driven by the formation of an intramolecular hydrogen bond between the amine hydrogen and the coordinated chloride; the N-H...Cl distance is 2.76 (6) angstrom, which is shorter than the expected van der Waals separation of 3.0 angstrom.

  DOI：

  10.1021/om00048a025