| 173009-83-1

• CAS: 173009-83-1
• 化学式: C₉H₂₇Cl₂O₁₀P₃W
• 分子量: 642.985
• InChiKey: WGTVQLNSNXHCTI-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.72
• 重原子数：
  25.0
• 可旋转键数：
  12.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  100.14
• 氢给体数：
  0.0
• 氢受体数：
  10.0

反应信息

• 作为反应物：
  描述：

  、 3,3-diphenylcyclopropene 以 苯 为溶剂， 以95%的产率得到W(η(2)-diphenylcyclopropene)Cl2(O)[P(OMe)3]2
  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

• Synthesis and characterization of tungsten oxo alkylidene complexes via the reaction of WCl2(O)[PX3]3 (PX3  P(OMe)3, PMe2Ph, PMePh2) with 4,8-dioxaspiro[2,5]oct-1-ene (ketalcyclopropene)
  作者：F. Javier de la Mata

  DOI：10.1016/s0022-328x(96)06493-5

  日期：1996.11

  This paper describes the synthesis and characterization of the first tungsten oxo ketalvinyl alkylidene complexes via the reaction of WCl2 (O)[PX3]3 (PX3  P(OMe)3 1, PMe2Ph 2, PMePh2 3 4,8-dioxaspiro[2,5]oct-1-ene (ketalcyclopropene). Complex 1 reacts with ketalcyclopropene affording almost quantitatively the corresponding s-cis-vinyl alkylidene complex W(CHCHCR(Cl2(O)[P(OMe)3] 4 (RCOCH2CH2CH2O−)

  本文描述的合成和表征所述第一钨氧代ketalvinyl亚烷基配合物经由WCL的反应2（O）[PX 3 ] 3（PX 3 P（OME）3 1，PME 2博士2，PMePh 2 3 4， 8-dioxaspiro [2,5] oct-1-ene（ketalcyclopropene）。配合物1与酮缩环丙烯反应，几乎定量提供相应的顺式-乙烯基亚烷基配合物W（CHCHCR（Cl 2（O）[P （OME）3 ] 4（RCOCH 2 CH 2 CH 2O-）。该络合物的NMR数据支持伪八面体结构，其中氧配体占据轴向位置。为了最大化π键，亚烷基配体必须与氧代配体顺式且螯合缩酮官能团被反式置于​​氧代配体上。P（OMe）3和氯化物配体位于赤道平面，P（OMe）3配体位于亚烷基配体的顺式位置。配合物2和3也与稍过量的缩酮环丙烯反应，得到采用不同配位方式的乙烯基亚烷基配合物。配合物4中的两个氯化物配体
• Some trimethyl phosphine and trimethyl phosphite complexes of tungsten(IV)
  作者：Ernesto Carmona、Luis Sánchez、Manuel L. Poveda、Richard A. Jones、John G. Hefner

  DOI：10.1016/s0277-5387(00)87209-5

  日期：1983.1

  Direct reduction of WCl6 with PMe3 in toluene at 120°C in a sealed tube affords the complexes [WCl4(PMe3)x] (x = 2, 3). [WCl4(PMe3)3] abstracts oxygen from equimolar amounts of water in wet acetone or tetrahydrofuran to give [WOCl2(PMe3)3] in very high yields. This procedure has been successfully applied to the high yield synthesis of other known oxotungsten(IV) complexes, [WOCl2(PR3)3] (PR3 = PMe2Ph

  在密封管中于120°C在甲苯中用PMe 3将WCl 6直接还原，得到配合物[WCl 4（PMe 3）x ]（x = 2，3）。[WCl 4（PMe 3）3 ]从湿丙酮或四氢呋喃中的等摩尔量的水中提取氧气，从而以非常高的收率得到[ WOCl 2（PMe 3）3 ]。此方法已成功应用于其他已知的氧钨（IV）配合物[WOCl 2（PR 3）3 ]（PR 3 = PMe 2Ph和PMePh 2）。[ WOCl 2（PMe 3）3 ]与NaX的复分解反应得到[WOX 2（PMe 3）3 ]（X = NCO，NCS）和[WOX 2（PMe 3）]（X = Me 2 NCS 2）。还描述了亚磷酸三甲酯类似物[WOCl 2（P（OMe）3）3 ]的合成，并基于IR和1 H和31 P NMR光谱确定了新配合物的结构。