fac-(cis-1,5-bis((diphenylphosphino)-(methyl))-3-oxabicyclo{3.3.0}octane-P,P',O)W(CO)3 | 134848-45-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: fac-(cis-1,5-bis((diphenylphosphino)-(methyl))-3-oxabicyclo{3.3.0}octane-P,P',O)W(CO)3
• 英文别名: [(3aS,6aR)-3a-(diphenylphosphanylmethyl)-3,4,5,6-tetrahydro-1H-cyclopenta[c]furan-6a-yl]methyl-diphenylphosphane;carbon monoxide;tungsten
• CAS: 134848-45-6
• 化学式: C₃₆H₃₄O₄P₂W
• 分子量: 776.461
• InChiKey: HMSYEYBRPAQJJQ-OIQUXJGDSA-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',O)W(CO)3 在 ⁽¹³⁾CO 作用下， 以 二氯甲烷-D2 为溶剂， 生成 fac-(cis-1,5-bis((diphenylphosphino)-methyl)-3-oxabicyclo{3.3.0}octane-P,P')tetracarbonyltungsten
  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：

  cis-1,5-bis{(diphenylphosphino)methyl}-3-oxabicyclo{3.3.0}octane 、 三羰基三甲苯铬 以 甲苯 为溶剂， 以64%的产率得到fac-(cis-1,5-bis((diphenylphosphino)-(methyl))-3-oxabicyclo{3.3.0}octane-P,P',O)W(CO)3
  参考文献：
  名称：

  Bidentate and tridentate coordination modes of a novel bicyclic ditertiary phosphine ether

  摘要：

  The synthesis and characterization of the new ligand cis-1,5-bis[(diphenylphosphino)methyl]-3-oxa-bicyclo[3.3.0]octane (6) is reported. Oxidation of 6 with t-BuOOH or S8 yields the phosphoryl and thiophosphoryl derivatives 10a and 10b, respectively. The complexes (6-P,P')M(CO)4 (M = Cr, Mo, W), (6-P,P')PdCl2, and two diastereomers of fac-(6-P,P')Mn(CO)3Br have been prepared, in which 6 coordinates in a bidentate (P,P') fashion. H-1 NMR spectra suggest a ligand conformational preference in these complexes. A tridentate (P,P',O) coordination mode has been established for (6-P,P',O)M(CO)3 (M = Mo, W) and [(6-P,P',O)Mn(CO)3]BF4 on the basis of H-1, C-13, P-31, and IR spectroscopic data. Single-crystal X-ray diffraction studies on (6-P,P')Mo(CO)4 and (6-P,P',O)W(CO)3 verify the bidentate and tridentate coordination modes of 6, respectively. Crystals of (6-P,P')Mo(CO)4 are triclinic, space group P1BAR, with unit cell dimensions a = 15.321 (3) angstrom, b = 22.371 (3) angstrom, c = 11.376 (2) angstrom, alpha = 90.52 (1)-degrees, beta = 91.80 (1)-degrees, gamma = 72.07 (1)-degrees, and Z = 4. Crystals of (6-P,P',O)W(CO)3 are monoclinic, space group P2(1)/c (No. 14), with unit cell dimensions a = 12.262 (5) angstrom, b = 17.38 (1) angstrom, c = 16.285 (7) angstrom, beta = 92.08 (4)-degrees, and Z = 4. The structures were refined to R = 0.059 and R(w) = 0.079 for 6702 reflections with I > 3.0-sigma-(I) for (6-P,P')Mo(CO)4 and R = 0.076 and R(w) = 0.093 for 4068 reflections with I greater-than-or-equal-to 3.0-sigma-(I) for (6-P,P',O)W(CO)3.

  DOI：

  10.1021/om00053a041

文献信息

• MASON, MARK R.;SU, YINGZHONG ;JACOBSON, ROBERT A.;VERKADE, JOHN G., ORGANOMETALLICS, 10,(1991) N, C. 2335-2344
  作者：MASON, MARK R.、SU, YINGZHONG 、JACOBSON, ROBERT A.、VERKADE, JOHN G.

  DOI：——

  日期：——