| 141273-50-9

• CAS: 141273-50-9
• 化学式: BF₄*C₂₃H₅₂O₅OsP₃
• 分子量: 778.589
• InChiKey: CKLYTOYAFYTAAU-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

• 作为产物：
  描述：

  、 三甲氧基磷 在 CH₃CN 作用下， 以 1,2-二氯乙烷 为溶剂， 以85%的产率得到
  参考文献：
  名称：

  八面体烷基氢os（II）配合物[OsH（R）（CO）2（PR'3）2]的合成，分子结构和反应活性。

  摘要：

  In contrast to the reaction of [OsH(eta-1-BH4)(CO)(PR'3)2] (2a,b) with methanol under reflux, which gives the dihydrides cis,cis,trans-[OsH2(CO)2(PR'3)2] (4a,b), the corresponding reaction with ethanol or 2-methoxyethanol under the same conditions leads to the formation of the alkylhydridoosmium(II) complexes [OsH(R)(CO)2(PR'3)2] (5a,b (R = CH3), 6a,b (R = MeOCH2)) in good yields. The X-ray structural analysis of 5a reveals an octahedral coordination sphere around the osmium center with the CO ligands in cis and the phosphines in trans positions. Reactions of 5a,b with electrophiles preferentially leads to cleavage of the Os-CH3 bond; thus, on treatment with HX (X = Cl, CH3CO2, CF3CO2) the monohydrides [OsHX(CO)2(PR'3)2] (11, 12, 13a,b) are formed. Protonation of 5a with HBF4 in ether/acetone yields quantitatively the cationic hydrido complex [OsH(acetone)(CO)2(PiPr3)2]BF4 (15) whereas from 5a,b and HBF4 in the presence of water the compounds [OsH(H2O)(CO)2(PR'3)2]BF4 (16a,b) are obtained. Complex 15 reacts with acetonitrile, trimethyl phosphite, or pyrazole by displacement of the acetone ligand to give the compounds [OsH(L)(CO)2(PiPr3)2]BF4 (17-19). Subsequent reaction of 19 (L = pyrazole) with the dimers [M(mu-OMe) (diolefin) ] 2 (20, 22, M = Rh; 2 1, M = Ir) produces the heterobinuclear complexes 23-25; in these the metal centers (Os and Rh or Ir) are bridged by a hydride and a pyrazolyl group. Treatment of 15 with methyl vinyl ketone and CO2Me-substituted alkynes RC=CO2Me gives cationic four- and five-membered metallacycles 26-29 which are formed by a Markovnikov or an anti-Markovnikov type of insertion of the unsaturated substrate into the Os-H bond.

  DOI：

  10.1021/om00042a018