bis(η(5)-methylcyclopentadienyl)bis(propynyl)zirconocene | 105036-32-6

• 英文名称: bis(η(5)-methylcyclopentadienyl)bis(propynyl)zirconocene
• 英文别名: bis(η5-methylcyclopentadienyl)bis(propynyl)zirconium；bis(η-methylcyclopentadienyl)dipropynylzirconium；bis(methylcyclopentadienyl)bis(propynyl)zirconium
• CAS: 105036-32-6
• 化学式: C₁₈H₂₀Zr
• 分子量: 327.581
• InChiKey: WVZLKTUJHYEKLR-UHFFFAOYSA-N

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：

  bis(η(5)-methylcyclopentadienyl)bis(propynyl)zirconocene 、 以 further solvent(s) 为溶剂， 以54%的产率得到
  参考文献：
  名称：

  Röttger, Dirk; Erker, Gerhard; Fröhlich, Roland, Journal of the American Chemical Society, 1995, vol. 117, # 42, p. 10503 - 10512

  摘要：

  DOI：
• 作为产物：
  描述：

  双(甲基环戊二烯)二氯化锆 、 丙基锂 以 乙醚 为溶剂， 以83%的产率得到bis(η(5)-methylcyclopentadienyl)bis(propynyl)zirconocene
  参考文献：
  名称：

  ‘Agostic’ metal–alkenyl β-CH interaction in (C₅H₄Me)₂ZrCl(CHCMe)ZrCl(C₅H₅)₂

  摘要：

  对于标题化合物 (C5H4Me)2ZrCl(CCHCMe)ZrCl(C5H5)2(7)，其通过 (C5H4Me)2ZrCl(CCMe)(6) 的氢化锆化制备，是一种“激动剂”锆“烯基β-” CH 相互作用通过 nmr 证明。和 X 射线衍射研究。

  DOI：

  10.1039/c39860000372

文献信息

• Dynamic features of the zirconocene-boron-betaine complexes obtained by treatment of bis(alkynyl)zirconocenes with the tris(pentafluorophenyl) borane Lewis-acid
  作者：Wolfgang Ahlers、Bodo Temme、Gerhard Erker、Roland Fröhlich、Thomas Fox

  DOI：10.1016/s0022-328x(96)06610-7

  日期：1997.1

  Bis(propynyl)zirconocene (6a) reacts with tris(pentafluorophenyl)borane to yield the carbon-carbon coupled Cp2M(μ-RC4R)B(C6F5)3 betaine product 4a (M  Zr, R  CH3). A variety of differently substituted analogs was prepared (M  Zr, R = n-butyl, phenyl, cyclohexyl; M  Ti, R  CH3; M  Hf; R  CH3, phenyl, SiMe3). These complexes 4 are chiral due to the presence of a rather stable propeller-like RB(aryl)3

  双（丙炔基）二茂锆（6A）反应与三（五氟苯基）硼烷，得到的碳-碳偶联的Cp 2 M（μ-RC 4 R）B（C 6 ˚F 5）3甜菜碱产品4A（M的Zr，R CH 3）。制备了各种不同取代的类似物（M 3 Zr，R =正丁基，苯基，环己基； M 3 Ti，R 3 CH 3； M 3 Hf； R 3 CH 3，苯基，SiMe 3）。由于存在相当稳定的螺旋桨状RB（芳基）3，这些配合物4是手性的构象。该系列配合物的许多例子的分子内对映体化过程的活化势垒是通过动态1 H NMR光谱法测定的，† G↕值范围约为。取决于取代模式，为13至16kcal mol -1。络合物4a与2，6-二甲基苯基异氰化物反应，得到通过X射线衍射表征的亚甲基环丙烯衍生物1。
• Evidence for a Carbon−Carbon Coupling Reaction To Proceed through a Planar-Tetracoordinate Carbon Intermediate
  作者：Gerhard Erker、Sabine Venne-Dunker、Gerald Kehr、Nina Kleigrewe、Roland Fröhlich、Christian Mück-Lichtenfeld、Stefan Grimme

  DOI：10.1021/om0495628

  日期：2004.9.1

  Treatment of bis(propynyl)zirconocene with B(C6F5)3 results in a linear C−C coupling of the alkynyl ligands to form the zwitterionic complex 3. Its treatment with excess RC⋮N yields an organometallic methylenecyclopropene derivative (6). This reaction topologically requires a very endothermic substituted butenyne to methylenecyclopropene cyclization to become energetically feasible by suitable stabilization

  用B（C 6 F 5）3处理双（丙炔基）锆茂金属导致炔基配体线性C-C偶联，形成两性离子络合物3。用过量的RC 3 N处理得到有机金属的亚甲基环丙烯衍生物（6）。该反应在拓扑上需要非常吸热的丁烯至亚甲基环丙烯环化，以通过适当的稳定作用在能量上可行。DFT研究表明，3 → 6 转化可能是由向金属中添加腈而形成的平面四配位碳中间体引发的，该中间体通过其碳-碳σ键之一配位三元碳环。
• Erker, Gerhard; Frömberg, Wolfgang; Benn, Reinhard, Organometallics, 1989, vol. 8, # 4, p. 911 - 920
  作者：Erker, Gerhard、Frömberg, Wolfgang、Benn, Reinhard、Mynott, Richard、Angermund, Klaus、Krüger, Carl

  DOI：——

  日期：——
• Reaction of (σ-alkynyl) Group 4 metallocene cation complexes with alkyl- and arylisocyanides
  作者：Wolfgang Ahlers、Gerhard Erker、Roland Fröhlich

  DOI：10.1016/s0022-328x(98)00871-7

  日期：1998.11

  The cations [(RCp)(2)M(-C=C-CH3)(THF)(+)] (2a-d) [(RCp)(2)M = Cp2Ti, Cp2Zr, (MeCp)(2)Zr, and Cp2Hf] were generated in situ by treatment of the respective bis(propynyl) Group 4 metallocenes (RCp)(2)M(-C=C-CH3)(2) (1a-d) with N,N-dimethylanilinium tetraphenylborate. Addition of excess tert-butylisocyanide gave the isonitrile insertion/addition products [(RCp)(2)M(eta(2)-Me3C-NC-C=C-CH3)(kappa-C=N-CMe3) +] (8a-d). Complex 8b was characterized by X-ray diffraction. It contains a eta(2)-iminoacyl ligand with N-inside orientation and there is a kappa-tert-butylisocyanide coordinated to the cationic metallocene framework. Complex 8b exhibits the typical structural characteristics of a d degrees-configurated isonitrile complex (bond lengths 2.350(4) and 1.148(4) Angstrom for the Zr-C=N-R unit). Insertion of 2,6-dimethylphenylisocyanide into the Zr-C(sp) sigma-bond of in situ generated [Cp2Hf-C-=C-CH3+] cation td leads to the formation of the analogous cationic hafnocene complex Se. (C) 1998 Elsevier Science S.A. All rights reserved.