W(2,6-diphenylphenoxide)2(EtC2Et)2 | 117774-63-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: W(2,6-diphenylphenoxide)2(EtC2Et)2
• 英文别名: 2,6-diphenylphenolate;hex-3-yne;tungsten(2+)
• CAS: 117774-63-7
• 化学式: C₄₈H₄₆O₂W
• 分子量: 838.742
• InChiKey: WKOLLZSFUPELPE-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  13.96
• 重原子数：
  51.0
• 可旋转键数：
  12.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  W(2,6-diphenylphenoxide)2(EtC2Et)2 以 氘代苯 为溶剂， 生成
  参考文献：
  名称：

  炔烃在单核芳氧化钨金属中心的配位和低聚

  摘要：

  Reduction of either [W(OC6H3Ph2-2,6)2Cl4] (OCH3Ph2-2,6 = 2,6-diphenylphenoxide) or [W(OC6H3Pri2-2,6)2Cl4] (OC6H3Pri2-2,6 = 2,6-diisopropylphenoxide) in toluene with sodium amalgam in the presence of alkynes (EtC=CEt; PhC=CPh; 4Me-PhC=CPh-4Me) leads to a series of alkyne (ac) adducts of general formulae [(ArO)2WCl2(ac)] (1) and [(ArO)2W(ac)2] (2). The C-13 NMR spectra of 1 and 2 show downfield shifts for the coordinated alkyne carbon atoms. A single crystal X-ray diffraction analysis shows five coordinate [W(OC6H3Ph2-2,6)2Cl2(C2Et2)] (1a) to adopt a square pyramidal geometry about tungsten with trans aryloxide ligands and an axial 3-hexyne. The solid state structure of [W(OC6H3Ph-2,6)2(C2Et2)2] (2a) shows a pseudo-tetrahedral environment about tungsten with the two 3-hexyne ligands arranged parallel with each other. Reaction of the eta6-arene complex [W(OC6H3Ph-eta6-C6H5)(OC6H3Ph2-2,6)(dppm)] with 3-hexyne generates the compound [W(OC6H3Ph2-2,6)2(C4Et4)] (3) which contains a tunptacyclopentatriene ring. This ring is nonplanar both in the solid state and solution (NMR). The bis-cyclometalated compounds [W(OC6H3Ph-C6H4)2(L)2] (L = PMe2Ph, PMePh2, and py) react with alkynes to form a number of products. From the reaction with 3-hexyne, two new compounds of formula [W(OC6H3PhC6H4)2(C4Et4)] (4) and [W(OC6H3PhC6H4)2(C6Et6)] (5) were isolated. Structural studies on 4 and 5 show them to contain multiple metallacyclic rings formed by transfer of one of the metalated aryloxide carbon atoms to an alpha-carbon of an intermediate tungstacyclopenta-2,4-diene complex. Crystal data at -100-degrees-C for WCl2O2C42H36 (1a): a = 9.331(2), b = 12.271(2), c = 16.334(3) angstrom; alpha = 107.48(1), beta = 101.78(2), gamma = 95.13(2)-degrees; Z = 2, d(calcd) = 1.595 g cm-3 in space group P1BAR; for WO2C48H46 (2a) at 20-degrees-C: a = 11.458(l), b = 17.961(4), c = 10.915(2) angstrom; alpha = 104.65(1), beta = 115.23(1), gamma = 92.08(1)-degrees; Z = 2, d(calcd) = 1.437 g CM-3 in ace group P1BAR; for WO2C48H46 (3) at -114-degrees-C: a = 11.086(2), b = 18.400(7), c = 19.453(5) angstrom alpha = 98.96(2), beta = 97.14(2), gamma = 98.67(2)-degrees; Z = 4, d(calcd) = 1.454 g cm-3 in space group P1BAR; for WO2C48H44 (4) at 20-degrees-C: a = 10.805(7), b = 11.662(1), c = 17.008(3) angstrom; alpha = 80.12(1), beta = 84.71(3), gamma = 63.07(3)-degrees; Z = 2, d(calcd) = 1.476 g cm-3 in space group Pi; for WO2C54H54 (5) at 20-degrees-C: a = 9.835(2), b = 11.8298(7), c = 19.620(2) angstrom; alpha = 104.748(6), beta = 98.717(9), gamma = 104.478-(8)-degrees; Z = 2, d(calcd) = 1.467 g cm-3 in space group P1BAR.

  DOI：

  10.1021/om00030a014
• 作为产物：
  描述：

  cis-WCl4(2,6-diphenylphenoxide) 、 3-己炔 在 Na#Hg 作用下， 以 甲苯 为溶剂， 以60%的产率得到W(2,6-diphenylphenoxide)2(EtC2Et)2
  参考文献：
  名称：

  炔烃在单核芳氧化钨金属中心的配位和低聚

  摘要：

  Reduction of either [W(OC6H3Ph2-2,6)2Cl4] (OCH3Ph2-2,6 = 2,6-diphenylphenoxide) or [W(OC6H3Pri2-2,6)2Cl4] (OC6H3Pri2-2,6 = 2,6-diisopropylphenoxide) in toluene with sodium amalgam in the presence of alkynes (EtC=CEt; PhC=CPh; 4Me-PhC=CPh-4Me) leads to a series of alkyne (ac) adducts of general formulae [(ArO)2WCl2(ac)] (1) and [(ArO)2W(ac)2] (2). The C-13 NMR spectra of 1 and 2 show downfield shifts for the coordinated alkyne carbon atoms. A single crystal X-ray diffraction analysis shows five coordinate [W(OC6H3Ph2-2,6)2Cl2(C2Et2)] (1a) to adopt a square pyramidal geometry about tungsten with trans aryloxide ligands and an axial 3-hexyne. The solid state structure of [W(OC6H3Ph-2,6)2(C2Et2)2] (2a) shows a pseudo-tetrahedral environment about tungsten with the two 3-hexyne ligands arranged parallel with each other. Reaction of the eta6-arene complex [W(OC6H3Ph-eta6-C6H5)(OC6H3Ph2-2,6)(dppm)] with 3-hexyne generates the compound [W(OC6H3Ph2-2,6)2(C4Et4)] (3) which contains a tunptacyclopentatriene ring. This ring is nonplanar both in the solid state and solution (NMR). The bis-cyclometalated compounds [W(OC6H3Ph-C6H4)2(L)2] (L = PMe2Ph, PMePh2, and py) react with alkynes to form a number of products. From the reaction with 3-hexyne, two new compounds of formula [W(OC6H3PhC6H4)2(C4Et4)] (4) and [W(OC6H3PhC6H4)2(C6Et6)] (5) were isolated. Structural studies on 4 and 5 show them to contain multiple metallacyclic rings formed by transfer of one of the metalated aryloxide carbon atoms to an alpha-carbon of an intermediate tungstacyclopenta-2,4-diene complex. Crystal data at -100-degrees-C for WCl2O2C42H36 (1a): a = 9.331(2), b = 12.271(2), c = 16.334(3) angstrom; alpha = 107.48(1), beta = 101.78(2), gamma = 95.13(2)-degrees; Z = 2, d(calcd) = 1.595 g cm-3 in space group P1BAR; for WO2C48H46 (2a) at 20-degrees-C: a = 11.458(l), b = 17.961(4), c = 10.915(2) angstrom; alpha = 104.65(1), beta = 115.23(1), gamma = 92.08(1)-degrees; Z = 2, d(calcd) = 1.437 g CM-3 in ace group P1BAR; for WO2C48H46 (3) at -114-degrees-C: a = 11.086(2), b = 18.400(7), c = 19.453(5) angstrom alpha = 98.96(2), beta = 97.14(2), gamma = 98.67(2)-degrees; Z = 4, d(calcd) = 1.454 g cm-3 in space group P1BAR; for WO2C48H44 (4) at 20-degrees-C: a = 10.805(7), b = 11.662(1), c = 17.008(3) angstrom; alpha = 80.12(1), beta = 84.71(3), gamma = 63.07(3)-degrees; Z = 2, d(calcd) = 1.476 g cm-3 in space group Pi; for WO2C54H54 (5) at 20-degrees-C: a = 9.835(2), b = 11.8298(7), c = 19.620(2) angstrom; alpha = 104.748(6), beta = 98.717(9), gamma = 104.478-(8)-degrees; Z = 2, d(calcd) = 1.467 g cm-3 in space group P1BAR.

  DOI：

  10.1021/om00030a014

文献信息

• KERSCHNER, JUDITH L.;FANWICK, PHILLIP E.;ROTHWELL, IAN P., J. AMER. CHEM. SOC., 110,(1988) N 24, C. 8235-8238
  作者：KERSCHNER, JUDITH L.、FANWICK, PHILLIP E.、ROTHWELL, IAN P.

  DOI：——

  日期：——