(η5-cyclopentadienyl)2Zr(η2-cyclohexyne)(trimethylphosphine)

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: (η5-cyclopentadienyl)2Zr(η2-cyclohexyne)(trimethylphosphine)
• 化学式: C₁₉H₂₇PZr
• 分子量: 377.621
• InChiKey: PYCRETBZAMBNQQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.96
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (η5-cyclopentadienyl)2Zr(η2-cyclohexyne)(trimethylphosphine) 在 N₂O 作用下， 以 甲苯 为溶剂， 以50-60的产率得到
  参考文献：
  名称：

  Oxygen-atom transfer from nitrous oxide. Synthesis and structure of a zirconocene oxametallacyclobutene complex

  摘要：

  DOI：

  10.1021/ja00229a047
• 作为产物：
  描述：

  、 三甲基膦 生成 (η5-cyclopentadienyl)2Zr(η2-cyclohexyne)(trimethylphosphine)
  参考文献：
  名称：

  环戊炔锆茂配合物的合成和 X 射线晶体结构及其在制备双环环戊烯酮中的应用

  摘要：

  La demethanation suvie d'unepyryse de Zr-(dimethyl-«5,5» cyclopentyl Zr-methyl zirconocene Fournit un Zr-di-η 5 -cyclopentadienyl dimethyl-3,3 zircona-1 bicyclo [3.1.0] hexene-2 (6) qui reagit ensuite avec un cyclohexyl-1 a​​llylmethyl ether puis est carbonyle pour donner un cyclohexylmethoxy-4dimethyl-8,8 bicyclo [3.3.0] octene 1(5) one-2

  DOI：

  10.1021/ja00207a025

文献信息

• .sigma.-Hydrocarbyl-bridged gallium/zirconium complexes containing planar-tetracoordinate carbon
  作者：Gerhard Erker、Markus Albrecht、Carl Krueger、Stefan Werner

  DOI：10.1021/ja00048a027

  日期：1992.10

  Several examples are described where in situ generated (eta2-alkyne) group 4 metallocene type substrates add to X-[M2] reagents (M2 = main group metal) to form dimetallabicyclic products Cp2M(mu-eta1:eta2-RCCR)(mu-X)[M2] which contain a planar-tetracoordinate carbon center in the mu-eta1:eta2-hydrocarbyl bridge. Thus, (eta2-cyclohexyne)(PMe3)ZrCp2 (4a) reacts in this way with excess trimethylgallium to give Cp2Zr(mu-eta1:eta2-C6H8)(mu-CH3)GaMe2 (6a). Complex 6a is one of the rare examples of a gallium compound containing sigma-hydrocarbyl bridges to this heavy main group metal. Complex 6a was characterized by X-ray diffraction. It crystallizes in space group P2(1)/c with cell parameters a = 9.007 (3) angstrom, b = 8.195 (2) angstrom, c = 25.404 (4) angstrom, beta = 91.30 (1)-degrees, Z = 4, R = 0.056, and R(w) = 0.066. Complex 6a contains a planar-tetracoordinate carbon atom C(2) with pertinent bond distances and angles of 2.423 (5) angstrom [Zr-C(2)], 2.096 (5) angstrom [Ga-C(2)], 1.572 (8) angstrom [C(2)-C(3)], 1.314 (7) angstrom [C(1)-C(2)], 119.5 (4)-degrees [C(3)-C(2)-C(1)], 100.3 (3)-degrees [C(3)-C(2)-Ga], 79.3 (1)-degrees [Ga-C(2)-Zr], and 61.1 (3)-degrees [C(1)-C(2)-Zr]. Both Cp rings are disordered. Zirconium and gallium seem to form a three-center two-electron bond with C(2). The planar-tetracoordinate geometry at carbon atom C(2) is probably electronically stabilized by the sigma-donor properties of the attached metal centers and by a pi-conjugative interaction of the C(2)-C(l)-Zr moiety normal to the sigma-plane. (Eta2-1,2-didehydrobenzene)(PMe3)ZrCp2 (4b) reacts analogously with trimethylgallium to give Cp2Zr(mu-eta1:eta2-C6H4)(mu-CH3)GaMe2 (6b) in almost quantitative yield. Complex 6b crystallizes isomorphously to the corresponding Al compound in space group P2(1)/n with cell parameters a = 9.126 (1) angstrom, b = 14.080 (2) angstrom, c = 14.323 (1) angstrom, beta = 103.88 (1)-degrees, Z = 4, R = 0.062, and R(w) = 0.038. It also contains a planar-tetracoordinate carbon atom [C(2)]. The reaction of Ph-C=C-GaMe2 (7) with (hydrido)zirconocene chloride produces Cp2Zr(mu-PhCCH)(mu-Cl)GaMe2 (9) which is probably also a similarly structured "anti-van't Hoff/LeBel complex". Complexes 6a and 6b react with ethylene or norbornene at room temperature with liberation of Me3Ga and formation of five-membered metallacyclic products (e.g., bis(eta-cyclopentadienyl)zirconaindane is obtained from 6b and ethylene).
• Synthesis, structure, and reactions of a zirconocene-cyclohexyne complex
  作者：Stephen L. Buchwald、Robert T. Lum、John C. Dewan

  DOI：10.1021/ja00283a068

  日期：1986.11
• Erker, Gerhard; Albrecht, Markus; Krüger, Carl, Organometallics, 1992, vol. 11, # 11, p. 3517 - 3525
  作者：Erker, Gerhard、Albrecht, Markus、Krüger, Carl、Werner, Stefan、Binger, Paul、Langhauser, Franz

  DOI：——

  日期：——
• Erker, Gerhard; Albrecht, Markus; Werner, Stefan, Chemische Berichte, 1992, vol. 125, # 8, p. 1953 - 1956
  作者：Erker, Gerhard、Albrecht, Markus、Werner, Stefan、Nolte, Matthias、Krueger, Carl

  DOI：——

  日期：——