WCl2(PhC2Ph)(PMe3)3 | 143281-03-2

• 英文名称: WCl2(PhC2Ph)(PMe3)3
• CAS: 143281-03-2
• 化学式: C₂₃H₃₇Cl₂P₃W
• 分子量: 661.224
• InChiKey: GGQSOUGKPNVMQG-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：

  WCl2(PhC2Ph)(PMe3)3 、 苯乙炔 以 苯 为溶剂， 生成
  参考文献：
  名称：

  The synthesis of octahedral mixed bis-alkyne and alkyne–alkene complexes of tungsten

  摘要：

  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)(CH2CH2)(PMe3)2] 的结构已通过 X 射线晶体学得到证实。

  DOI：

  10.1039/c39920001069
• 作为产物：
  描述：

  WCl3(PhC2Ph)(PMe3)2 、 三甲基膦 在 Na amalgam 作用下， 以 not given 为溶剂， 以>69的产率得到WCl2(PhC2Ph)(PMe3)3
  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

• 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.
• Diphenylacetylene complexes of tungsten containing π-acceptor ligands
  作者：George R. Clark、Alastair J. Nielson、A. David Rae、Clifton E. F. Rickard

  DOI：10.1039/dt9940001783

  日期：——

  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.