Cp₂Zr(C₆H₄)(PMe₃)

• 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: Cp₂Zr(C₆H₄)(PMe₃)
• 英文别名: (η5-cyclopentadienyl)2Zr(η2-C6H4)(trimethylphosphine)
• 化学式: C₁₉H₂₃PZr
• 分子量: 373.589
• InChiKey: AQTYHYPWMXMJRD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.69
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.16
• 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：

  Cp₂Zr(C₆H₄)(PMe₃) 在 CH₃OH 作用下， 生成 phenyl zirconocene methoxide
  参考文献：
  名称：

  Trimethylphosphine adduct of the zirconocene-benzyne complex: synthesis, reactions, and x-ray crystal structure

  摘要：

  DOI：

  10.1021/ja00283a048
• 作为产物：
  描述：

  diphenylbis(η5-cyclopentadienyl)-zirconium(IV) 、 三甲基膦 以 苯 为溶剂， 生成 Cp₂Zr(C₆H₄)(PMe₃)
  参考文献：
  名称：

  Trimethylphosphine adduct of the zirconocene-benzyne complex: synthesis, reactions, and x-ray crystal structure

  摘要：

  DOI：

  10.1021/ja00283a048

文献信息

• Insertion of sodium phosphaethynolate, Na[OCP], into a zirconium–benzyne complex
  作者：Jerod M. Kieser、Robert J. Gilliard, Jr.、Arnold L. Rheingold、Hansjörg Grützmacher、John D. Protasiewicz

  DOI：10.1039/c7cc01482a

  日期：——

  Reaction of the zirconium–benzyne complex [Cp2Zr(PMe3)(C6H4)] with sodium phosphaethynolate, Na[OCP], affords a zircono-phosphaalkene complex. Notably, unlike reactions of other transition metal complexes with Na[OCP] that yield the products of simple salt metathesis, this transformation represents novel Na[OCP] insertion chemistry and formation of an unusual solid state coordination polymer. The polymer

  锆-联苯胺络合物[Cp 2 Zr（PMe 3）（C 6 H 4）]与磷胸腺酸钠Na [OCP]的反应，得到锆-磷杂烯烃。值得注意的是，与其他过渡金属配合物与Na [OCP]的反应产生简单的盐复分解的产物不同，该转变代表了新颖的Na [OCP]插入化学反应和不寻常的固态配位聚合物的形成。加入Me 3 SiCl会破坏聚合物，从而提供保留了锆磷酸正链烯官能团的甲硅烷基封端的二聚体。两种形式的锆磷烷基烯烃的质子化导致形成苯甲酰基膦PhC（O）PH 2。
• Binger, Paul; Mueller, Patrik; Langhauser, Franz, Chemische Berichte, 1993, vol. 126, # 7, p. 1541 - 1550
  作者：Binger, Paul、Mueller, Patrik、Langhauser, Franz、Sandmeyer, Frank、Philipps, Petra、et al.

  DOI：——

  日期：——
• .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).
• 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：——
• Trimethylphosphine adduct of the zirconocene-benzyne complex: synthesis, reactions, and x-ray crystal structure
  作者：Stephen L. Buchwald、Brett T. Watson、John C. Huffman

  DOI：10.1021/ja00283a048

  日期：1986.11