dichlorobis(methyldiphenylphosphine-P)[(1,2-η)-3,3-diphenylcyclopropene]oxotungsten | 172952-29-3

• 英文名称: dichlorobis(methyldiphenylphosphine-P)[(1,2-η)-3,3-diphenylcyclopropene]oxotungsten
• 英文别名: W(η(2)-diphenylcyclopropene)Cl2(O)[PMePh2]2
• CAS: 172952-29-3
• 化学式: C₄₁H₃₈Cl₂OP₂W
• 分子量: 863.456
• InChiKey: WUYIDKISPONNNH-UHFFFAOYSA-L

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：

  1,1,1,3,3,3-hexafluoro-2-methylpropoxylithium 、 dichlorobis(methyldiphenylphosphine-P)[(1,2-η)-3,3-diphenylcyclopropene]oxotungsten 以 苯 为溶剂， 以65%的产率得到
  参考文献：
  名称：

  Synthesis and Reactions of Tungsten Oxo Vinylalkylidene Complexes:  Reactions of WCl₂(O)(PX₃) (X = OMe, R) Precursors with 3,3-Diphenylcyclopropene

  摘要：

  Complexes of the type WCl2(O)[PX(3)](3) (PX(3) = P(OMe)(3) (1); PMePh(2) (2)) were synthesized according to procedures previously described in the literature. Upon treatment with 3,3-diphenylcyclopropene, complexes 1 and 2 afforded the corresponding eta(2)-cyclopropene complexes. Spectroscopic data of W(eta(2)-diphenylcyclopropene)Cl-2(O)[PX(3)](2) (PX(3) = P(OMe)(3) (4); PMePh(2) (5)) were consistent with an octahedral geometry in which the two mutually trans PX(3) ligands and the cyclopropene ligand occupy equatorial positions cia to the apical oxo ligand. The;thermal rearrangement of the eta(2)-cyclopropene complexes leads to the dimerization product of 3,3-diphenylcyclopropene: 1,1,6,6-tetraphenyl-1,3,5-hexatriene. The presence of carbene species before the dimerization occurs has been demonstrated. Upon treatment with 2 equiv of lithium hexafluoro-tert-butoxide, complexes 4 and 5 give the vinyl alkylidene complexes W(=CHCH=CPh(2))(O)[OC(CH3)(CF3)(2)](2)[PX(3)] (PX(3) = P(OMe)(3) (10); PMePh(2)(7)). The spectroscopic data of 10 and 7 indicated a distorted trigonal bipyramid, where the oxo and alkylidene ligands are cis to each other and placed in the equatorial plane.

  DOI：

  10.1021/om950389c
• 作为产物：
  描述：

  [WCl2O(PMePh2)3] 、 3,3-diphenylcyclopropene 以 苯 为溶剂， 以90%的产率得到dichlorobis(methyldiphenylphosphine-P)[(1,2-η)-3,3-diphenylcyclopropene]oxotungsten
  参考文献：
  名称：

  Synthesis and Reactions of Tungsten Oxo Vinylalkylidene Complexes:  Reactions of WCl₂(O)(PX₃) (X = OMe, R) Precursors with 3,3-Diphenylcyclopropene

  摘要：

  Complexes of the type WCl2(O)[PX(3)](3) (PX(3) = P(OMe)(3) (1); PMePh(2) (2)) were synthesized according to procedures previously described in the literature. Upon treatment with 3,3-diphenylcyclopropene, complexes 1 and 2 afforded the corresponding eta(2)-cyclopropene complexes. Spectroscopic data of W(eta(2)-diphenylcyclopropene)Cl-2(O)[PX(3)](2) (PX(3) = P(OMe)(3) (4); PMePh(2) (5)) were consistent with an octahedral geometry in which the two mutually trans PX(3) ligands and the cyclopropene ligand occupy equatorial positions cia to the apical oxo ligand. The;thermal rearrangement of the eta(2)-cyclopropene complexes leads to the dimerization product of 3,3-diphenylcyclopropene: 1,1,6,6-tetraphenyl-1,3,5-hexatriene. The presence of carbene species before the dimerization occurs has been demonstrated. Upon treatment with 2 equiv of lithium hexafluoro-tert-butoxide, complexes 4 and 5 give the vinyl alkylidene complexes W(=CHCH=CPh(2))(O)[OC(CH3)(CF3)(2)](2)[PX(3)] (PX(3) = P(OMe)(3) (10); PMePh(2)(7)). The spectroscopic data of 10 and 7 indicated a distorted trigonal bipyramid, where the oxo and alkylidene ligands are cis to each other and placed in the equatorial plane.

  DOI：

  10.1021/om950389c

文献信息

• A Diphenylcyclopropene Complex of Tungsten, [WCl2O(PMePh2)2(η2-3,3-diphenylcyclopropene)], Precursor to a Tungsten–Oxo–Olefin Metathesis Catalyst
  作者：M. W. Day、T. E. Wilhelm、R. H. Grubbs

  DOI：10.1107/s0108270196006464

  日期：1996.10.15

  The title compound, dichlorobis(methyldiphenylphosphine-P)[(1,2-eta)-3,3-diphenylcyclopropene]oxotungsten, [WCl2O(C15H12)(C13H13P)(2)], is a mononuclear complex with an approximately octahedral environment around the metal atom. The 3,3-diphenylcyclopropene ligand is bonded to the W atom in a eta(2)-geometry, with effectively identical metal-to-carbon bond distances [W-C1 2.133 (7) and W-C2 2.131 (7) Angstrom].