| 164588-97-0

• CAS: 164588-97-0
• 化学式: C₄₀H₇₀ClO₃P₄SiTa
• 分子量: 967.375
• InChiKey: IRQNMMFEUBHIJL-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

• 作为产物：
  描述：

  、 乙酰氯 以 乙二醇二甲醚 为溶剂， 以64%的产率得到
  参考文献：
  名称：

  低价Ⅴ族二羰基膦配合物与碳基亲电试剂的反应，生成金属烷基，酰基，卡宾和乙炔配合物

  摘要：

  The [V(CO)(2)(dmpe)(2)](-) anion reacts with Et(3)OBF(4) and EtOTf to afford the unexpected product of formal C-alkylation, [V(eta(2)-C(O)Et)(CO)(dmpe)(2)], which has been structurally characterized by X-ray crystallography (space group Pna2(1), a = 12.917(2) Angstrom, b = 12.335(2) Angstrom c = 14.331(2) Angstrom, V = 2283.4(5) Angstrom(3)). The formation of species derived by O-acylation of the CO ligands in the [Ta(CO)(2)(dmpe)(2)](-) and [Ta(CO)(2)(depe)(2)](-) anions was indirectly established by isolation and characterization of products in which two CO ligands had coupled to form acetylene complexes. Addition of 2 equiv of acetyl chloride to Na[Ta(CO)(2)(dmpe)(2)] or Na[Ta(CO)(2)(depe)(2)] yielded the acetylene complexes [Ta(AcOC=COAc)(dmpe or depe)(2)Cl]. The structure of the dmpe derivative was confirmed in a single-crystal X-ray determination (space group C2, a = 14.964(2) Angstrom, b = 11.960(2) Angstrom, c = 31.710(5) Angstrom, beta = 102.77(1)degrees, V = 5535(1) Angstrom(3)). Additional proof of direct alkylation at terminal CO ligands was provided by isolation of mixed siloxy/alkoxyacetylene coupled products [M(R(3)(')SiOC=COR)(dmpe)(2)X] (R = Et, Ac, CO(2)Me; R'Si-3 = (t)BuPh(2)Si, (Pr3Si)-Pr-i) and [M(R'3SiOC=COR)(depe)(2)X] (R = Et, Ac; R'Si-3 = (t)BuPh(2)Si, (Pr3Si)-Pr-i, Me(3)Si) from reactions of the siloxycarbyne precursors [M(COSiR'(3))-(CO)(dmpe)(2)] and [M(COSiR'(3))(CO)(depe)(2)] (M = Nb, Ta) with carbon-based electrophiles. The proper choice of carbon-based electrophile and reaction conditions is crucial in order to avoid oxidation of these low-valent metal complexes to [M(CO)(2)(dmpe)(2)X], which can occur competitively or exclusively.

  DOI：

  10.1021/om00005a018