WCl2(PhC2Ph)(CO)(PMe3)2 | 158080-00-3

• 英文名称: WCl2(PhC2Ph)(CO)(PMe3)2
• CAS: 158080-00-3
• 化学式: C₂₁H₂₈Cl₂OP₂W
• 分子量: 613.156
• InChiKey: DSFLBHHSUKEGCT-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

• 作为产物：
  描述：

  WCl3(PhC2Ph)(PMe3)2 在 Na#Hg 、 CO 作用下， 以 苯 为溶剂， 以72%的产率得到WCl2(PhC2Ph)(CO)(PMe3)2
  参考文献：
  名称：

  Diphenylacetylene complexes of tungsten containing π-acceptor ligands

  摘要：

  Reaction of PhC2Ph with [WCI2(PhC2Ph)(PMe3)3] gave [WCI2(PhC2Ph)2(PMe3)2] 1 for which IR and NMR spectral data indicated cis-chloro ligands. trans phosphines and mutually-cis diphenylacetylene ligands. This geometry was confirmed by X-ray crystallography. The average W-C bond lengths are 2.071 (3) angstrom. The C-13 NMR spectrum showed the acetylenic carbon resonance at delta 185.45. The alkynes HC2H and PhC2H reacted with [WCI2(PhCPh)(PMe3)3] giving [WCl2(PhC2Ph)(HC2H)(PMe3)2] 2 and [WCl2(PhC2Ph)(PhC2H)(PMe3)2] 3. The phenylacetylene ligand gave rise to asymmetry in complex 3 leading to an AB system P-31-{H-1} NMR spectrum. Different values of 1J(PW) indicated small differences in the W-P bonding. Alkyl-substituted acetylenes did not react cleanly with [WCl2(PhC2Ph)(PMe3)3]. The complexes [WCl2(PhC2Ph)(PrC2Me)(PMe3)2] 4 and [WCl2(PhC2Ph)(MeC2Me)(PMe3)2] 5 were prepared by sodium-mercury amalgam reduction of [WCl3(PhC2Ph)(PMe3)2] with hex-2-yne or but-2-yne present but were not particularly stable in solution. Sodium-mercury amalgam reduction of [WCI3(PhC2Ph)(PMe3)2] under ethylene or propene gave [WCl2(PhC2Ph)(CH2CH2)(PMe3)2] 6 or [WCI2(PhC2Ph)(MeCHCH2)(PMe3)2] 9. Complex 9 was unstable in solution and was characterised by NMR spectroscopy. The C-13 NMR acetylenic carbon resonances in complexes 6 and 9 are at delta 218.11 and 218.82. Reduction of [WCI3(PhC2Ph)(PMe3)2] under cis- or trans-but-2-ene or 2-methyl propene afforded [WCl2(PhC2Ph)(PMe3)3] and [WCl2(PhC2Ph)(PMe3)2]x 10 as characterised by NMR spectroscopy. Reduction of [WCI3(PhC2Ph)L2] (L = PMe3 or PMePh2) under CO gave [WCI2(PhC2Ph)(CO)(PMe3)2] 11 and [WCl2(PhC2Ph)(CO)(PMePh2)2] 12 for which X-ray crystal structure determinations showed cis-chloro ligands, trans phosphines and mutually-cis PhC2Ph and CO ligands. The W-C and C-C bond lengths for complex 11 are 2.009(5), 2.024(5) and 1.341(6) angstrom, respectively. Overall the reactions showed that the diphenylacetylene ligand in these complexes acts like an organoimido or oxo ligand.

  DOI：

  10.1039/dt9940001783