WCl3(PhC2Ph)(PMe3)2 | 143281-01-0

• 英文名称: WCl3(PhC2Ph)(PMe3)2
• CAS: 143281-01-0
• 化学式: C₂₀H₂₈Cl₃P₂W
• 分子量: 620.599
• InChiKey: HDSQTMBHHZQJBU-UHFFFAOYSA-K

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：

  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
• 作为产物：
  描述：

  、 三甲基膦 在 sodium amalgam 作用下， 以 苯 为溶剂， 生成 WCl3(PhC2Ph)(PMe3)2
  参考文献：
  名称：

  钨的高价二苯基乙炔配合物

  摘要：

  W（4楼7 // 2）结合的能量[{WCL 4（PHC 2 PH）} 2 ] 1通过X射线光电子光谱法获得类似于[{WCL的4（NPH）} 2 ]，并与广告一致ö钨（VI）中的制剂。配合物1和[NEt 4 ] [WCl 5（PhC 2 Ph）] 2与NaOH-EtOH的反应生成顺-sti，表明大量电子从金属转移至配位炔。在存在膦的情况下用2当量的钠-汞齐汞盐还原配合物1，得到配合物[WCl 3（PhC 2 Ph）L 2 ]（L = PMe 3，PMe 2 Ph或PMePh 2），具有磁矩和W（4f7 // 2）结合能类似于d 1钨（V）有机亚氨基配合物[WCl 3（NPh）（PMe 3）2 ]的结合能。再次用NaOH-EtOH分解炔烃配合物，得到顺式-sti。已经确定了[WCl 3（PhC 2 Ph）（PMe 3）2 ] 3的晶体结构。W–Cl键反式传递至炔配体很长[2.479（3）Å]，而W–C键长度[2

  DOI：

  10.1039/dt9950001153

文献信息

• The synthesis of octahedral mixed bis-alkyne and alkyne–alkene complexes of tungsten
  作者：George R. Clark、Alastair J. Nielson、A. David Rae、Clifton E. F. Rickard

  DOI：10.1039/c39920001069

  日期：——

  Replacement of a phosphine ligand in [WCl2(PhC2Ph)(PMe3)3] by PhCCPh, PhCCH and HCCH, or reduction of [WCl3(PhC2Ph)(PMe3)2] in the presence of MeC2Me and Me(CH2)2C2Me yields mixed bis-alkyne complexes; under ethylene or propene the reduction reactions afford mixed alkyne–alkene complexes, and the structure of [WCl2(PhC2Ph)(CH2CH2)(PMe3)2] has been confirmed by X-ray crystallography.

  用 PhCCPh、PhCCH 和 HCCH 取代 [WCl2(PhC2Ph)(PMe3)3]中的膦配体，或在 MeC2Me 和 Me(CH2)2C2Me 存在下还原 [WCl3(PhC2Ph)(PMe3)2]，可得到混合双炔络合物；在乙烯或丙烯条件下，还原反应生成混合炔烃络合物，[WCl2(PhC2Ph)( )(PMe3)2] 的结构已通过 X 射线晶体学得到证实。
• Evidence for high oxidation state character in tungsten alkyne complexes
  作者：Alastair J. Nielson、Peter D.W. Boyd、George R. Clark、Tricia A. Hunt、James B. Metson、Clifton E.F. Rickard、Peter Schwerdtfeger

  DOI：10.1016/s0277-5387(00)83375-6

  日期：1992.1

  Synthetic, spectroscopic and structural analogies to organoimido complexes and theoretical calculations indicate the alkyne complexes [WCl4(PhC2Ph)]2, [WCl3(PhC2Ph)(P)2] and [WCl2(PhC2Ph)(P)3] (P = phosphine) have properties similar to d0, d1 and d2 tungsten complexes.