fac-(cis-1,5-bis((diphenylphosphino)-methyl)-3-oxabicyclo{3.3.0}octane-P,P')tricarbonyl(acetonitrile)tungsten | 139344-53-9

• 英文名称: fac-(cis-1,5-bis((diphenylphosphino)-methyl)-3-oxabicyclo{3.3.0}octane-P,P')tricarbonyl(acetonitrile)tungsten
• CAS: 139344-53-9
• 化学式: C₃₈H₃₇NO₄P₂W
• 分子量: 817.514
• InChiKey: STBNIDKHMAAGKF-KIIXEKCASA-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：

  fac-(cis-1,5-bis((diphenylphosphino)-methyl)-3-oxabicyclo{3.3.0}octane-P,P')tricarbonyl(acetonitrile)tungsten 在 氘代乙腈 作用下， 以 二氯甲烷 为溶剂， 生成 fac-(cis-1,5-bis((diphenylphosphino)-methyl)-3-oxabicyclo{3.3.0}octane-P,P')tricarbonyl(NCCD3)tungsten
  参考文献：
  名称：

  新型双环二叔膦醚的6族金属羰基配合物中的配体取代反应

  摘要：

  The complexes fac-(1-P,P',O)M(CO)3, where M = Mo or W and 1 is cis-1,5-bis((diphenylphosphino)-methyl)-3-oxabicyclo[3.3.0]octane, were found to react with the ligands L = acetonitrile, piperidine, pyridine, and P(OCH2)3CCH3 to yield two diastereomers of fac-(1-P,P')M(CO)3(L) in each case. H-1 and C-13 NMR spectroscopic data suggest that the major isomer in each product is that in which the added ligand occupies the site originally occupied by the ether oxygen of 1 and that the minor isomer contains the new ligand in the position trans to this site. Carbon monoxide reacts with the complexes fac-(1-P,P',O)M(CO)3 (M = Mo, W) to yield (1-P,P')M(CO)4. Using (CO)-C-13, these reactions stereoselectively yield two diastereomers of fac-(1-P,P')M(CO)3((CO)-C-13) in ratios of approximately 5:1 and 7:1 for M = Mo and W, respectively. A scheme involving the isomerization of diastereomeric five-coordinate square-pyramidal intermediates is discussed. The N-donor complexes fac-(1-P,P')M(CO)3L, where M = Mo and W and L = acetonitrile, pyridine, and piperidine, were observed by infrared and H-1 and P-31 NMR spectroscopy to partially dissociate in solution, equilibrating with free L and fac-(1-P,P',O)M(CO)3. This equilibrium was further substantiated by monitoring the exchange reaction between free and coordinated CD3CN in the presence of fac-(1-P,P')Mo(CO)3(NCCH3) using H-2 NMR spectroscopy.

  DOI：

  10.1021/om00040a022
• 作为产物：
  描述：

  fac-(cis-1,5-bis((diphenylphosphino)-(methyl))-3-oxabicyclo{3.3.0}octane-P,P',O)W(CO)3 在 乙腈 作用下， 以 二氯甲烷 为溶剂， 生成 fac-(cis-1,5-bis((diphenylphosphino)-methyl)-3-oxabicyclo{3.3.0}octane-P,P')tricarbonyl(acetonitrile)tungsten 、 fac-(cis-1,5-bis((diphenylphosphino)-methyl)-3-oxabicyclo{3.3.0}octane-P,P')tricarbonyl(acetonitrile)tungsten
  参考文献：
  名称：

  新型双环二叔膦醚的6族金属羰基配合物中的配体取代反应

  摘要：

  The complexes fac-(1-P,P',O)M(CO)3, where M = Mo or W and 1 is cis-1,5-bis((diphenylphosphino)-methyl)-3-oxabicyclo[3.3.0]octane, were found to react with the ligands L = acetonitrile, piperidine, pyridine, and P(OCH2)3CCH3 to yield two diastereomers of fac-(1-P,P')M(CO)3(L) in each case. H-1 and C-13 NMR spectroscopic data suggest that the major isomer in each product is that in which the added ligand occupies the site originally occupied by the ether oxygen of 1 and that the minor isomer contains the new ligand in the position trans to this site. Carbon monoxide reacts with the complexes fac-(1-P,P',O)M(CO)3 (M = Mo, W) to yield (1-P,P')M(CO)4. Using (CO)-C-13, these reactions stereoselectively yield two diastereomers of fac-(1-P,P')M(CO)3((CO)-C-13) in ratios of approximately 5:1 and 7:1 for M = Mo and W, respectively. A scheme involving the isomerization of diastereomeric five-coordinate square-pyramidal intermediates is discussed. The N-donor complexes fac-(1-P,P')M(CO)3L, where M = Mo and W and L = acetonitrile, pyridine, and piperidine, were observed by infrared and H-1 and P-31 NMR spectroscopy to partially dissociate in solution, equilibrating with free L and fac-(1-P,P',O)M(CO)3. This equilibrium was further substantiated by monitoring the exchange reaction between free and coordinated CD3CN in the presence of fac-(1-P,P')Mo(CO)3(NCCH3) using H-2 NMR spectroscopy.

  DOI：

  10.1021/om00040a022