zirconocene hydrochloride | 37342-97-5

• 物质功能分类: 有机原料 - 有机金属类化合物 - 有机锆
• 分子结构分类: 有机化合物 - 碳氢化合物 - 芳香烃
• 英文名称: zirconocene hydrochloride
• 英文别名: Zr(Cp)2*HCl；dicyclopentadienylzirconium hydrochloride；Cp2ZrHCl；Zirconocene hydrochloride；cyclopenta-1,3-diene;zirconium(2+);hydrochloride
• CAS: 37342-97-5
• 化学式: C₁₀H₁₀Zr*ClH
• 分子量: 257.874
• InChiKey: QIGBZGQZFNVXIS-UHFFFAOYSA-N

物化性质

• 熔点：
  300 °C
• 暴露限值：
  ACGIH: TWA 5 mg/m3; STEL 10 mg/m3NIOSH: IDLH 25 mg/m3; TWA 5 mg/m3; STEL 10 mg/m3

计算性质

• 辛醇/水分配系数(LogP)：
  3.23
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  1
• 氢受体数：
  2

安全信息

• 危险等级：
  4.3
• 危险品标志：
  C
• 安全说明：
  S16,S26,S27,S36/37/39,S45,S8
• 危险类别码：
  R34,R15,R11
• WGK Germany：
  3
• 海关编码：
  2903890090
• 危险品运输编号：
  UN 3131 4.3/PG 2
• 危险类别：
  4.3
• 包装等级：
  II

制备方法与用途

简介

茂金属（metallocene），即两个环戊二烯基(Cp-)或其衍生物以平面共轭π键的形式与金属的卤化物成键所形成的金属有机配合物。近年来，桥联二茂锆配合物引起了金属有机化学家的兴趣，这主要是因为它们在结构和反应性能上与非桥联二茂锆化合物相比具有独特之处。氢氯二茂锆是应用较多的一种桥联二茂锆配合物。

用途

氢氯二茂锆是一种有机中间体，可用于制备1-氮杂-5-锡杂-5-氯二环[3.3.3]十一烷化合物。

制备

将二氯二茂锆（31 mmol）称入Schlenk瓶中，在真空线上充换氩气三次。随后加入无水四氢呋喃（70 mL），直至固体完全溶解。接着，溶剂无水四氢呋喃中滴加氢化铝锂（10 mmol，由梯希爱化成工业发展有限公司提供），在惰性气体氛围下缓慢加入Schlenk瓶中。滴加结束后，在室温下搅拌3.5小时后抽滤分离得到白色固体氢氯二茂锆，收率为85%。

反应信息

• 作为反应物：
  描述：

  zirconocene hydrochloride 、 Dimethyl 4,4-bis[di(propan-2-yl)amino]-1,2,3-triaza-4lambda5-phosphacyclohexa-2,4,6-triene-5,6-dicarboxylate 以 四氢呋喃 为溶剂， 以45%的产率得到
  参考文献：
  名称：

  Ligand Behavior of a (Z)-Phosphazide (a 1,2,3,4λ⁵-Triazaphosphinine) and of the Corresponding Phosphazene (a 1,2λ⁵-Azaphosphete)

  摘要：

  1,2,3,4 lambda(5)-Triazaphosphinine 1 reacts with PdCl2(PhCN)(2) and W(CO)(5)(THF) at room temperature, affording, according to P-31 NMR spectroscopy, eta(1)-triazaphosphinine complexes 3 and 5, which after elimination of dinitrogen give the bis(eta(1)-azaphosphete)palladium(II) complex 4 and (eta(1)-azaphosphete)W(CO)(5) complex 6, in 65% and 88% yield, respectively. Complex 4 can also be obtained in 90% yield by addition of PdCl2(PhCN)(2) to 1,2 lambda(5)-azaphosphete 2. Addition of cis-Mo(CO)(4)(pip)(2) to 1 leads to (eta(1)-triazaphosphinine)Mo(CO)(4)(pip) complex 7, which was isolated in 70% yield. In solution, at room temperature for 2 days, 7 transforms into to eta(1)-(five-membered cyclophosphazene)Mo(CO)(5) complex 9 in 45% yield. When 2 equiv of W(CO)(5)(pip) is added to 1, complex 10 featuring a five-membered cyclophosphazene bonded to W(CO)(5)(pip) via a hydrogen bond is isolated in 80% yield. 1,2 lambda(5)-Azaphosphete 2 reacts with piperidine, affording five-membered phosphazene ring 11 in 95% yield, which by subsequent treatment with Mo(CO)(5)(pip) and W(CO)(5)(pip) gives complexes 9 (75% yield) and 10 (83% yield), respectively. Schwartz's reagent reacts with 1, affording five-membered zirconacyclophosphazene 12 in 45% yield. Complexes 4, 7, 10, and 12 are characterized by single-crystal X-ray analyses. These results as a whole demonstrate that in contrast with (E)-phosphazides which behave as four-electron donors via the alpha- and gamma-nitrogen atoms and which are stabilized by complexation, (Z)-phosphazides, such as the 1,2,3,4 lambda(5)-triazaphosphinine 1, act as two-electron donors via the beta-nitrogen atom, and are destabilized by the metal with respect to nitrogen elimination.

  DOI：

  10.1021/ja9531440
• 作为试剂：
  描述：

  (S)-1-辛炔-3-醇 、 叔丁基二甲基氯硅烷 在 咪唑 、 zirconocene hydrochloride 作用下， 以 二氯甲烷 为溶剂， 反应 25.25h， 生成 (1E,3S)-1-iodo-3-(tert-butyldimethylsiloxy)-1-octene
  参考文献：
  名称：

  [EN] COMPOUND AND METHOD
  [FR] COMPOSÉ ET PROCÉDÉ

  摘要：

  公式（I）的化合物：（I）其中Y是，Z是OR10，NR11R11 SR11，S（0）R11 S02R11，R10是H，可选地取代的烷基，可选地取代的环烷基，可选地取代的烯基，可选地取代的炔基，可选地取代的芳基，可选地取代的杂环芳基，可选地取代的杂环烷基，CO-R11或保护基，R11是可选地取代的烷基，可选地取代的环烷基，可选地取代的烯基，可选地取代的炔基，可选地取代的芳基，可选地取代的杂环芳基，可选地取代的杂环烷基或烷氧基；制备公式（I）的化合物的方法；以及使用公式（I）的化合物制备前列腺素或前列腺素类似物的方法。

  公开号：

  WO2013186550A1

文献信息

• Reaction of metallocene dichlorides of titanium(IV) and zirconium(IV) with lithium bis(trimethylsilyl)amide
  作者：Stephen J. Simpson、Richard A. Andersen

  DOI：10.1021/ic50225a009

  日期：1981.11
• Ligand Behavior of a (<i>Z</i>)-Phosphazide (a 1,2,3,4λ⁵-Triazaphosphinine) and of the Corresponding Phosphazene (a 1,2λ⁵-Azaphosphete)
  作者：Klaus Bieger、Ghenwa Bouhadir、Régis Réau、Françoise Dahan、Guy Bertrand

  DOI：10.1021/ja9531440

  日期：1996.1.1

  1,2,3,4 lambda(5)-Triazaphosphinine 1 reacts with PdCl2(PhCN)(2) and W(CO)(5)(THF) at room temperature, affording, according to P-31 NMR spectroscopy, eta(1)-triazaphosphinine complexes 3 and 5, which after elimination of dinitrogen give the bis(eta(1)-azaphosphete)palladium(II) complex 4 and (eta(1)-azaphosphete)W(CO)(5) complex 6, in 65% and 88% yield, respectively. Complex 4 can also be obtained in 90% yield by addition of PdCl2(PhCN)(2) to 1,2 lambda(5)-azaphosphete 2. Addition of cis-Mo(CO)(4)(pip)(2) to 1 leads to (eta(1)-triazaphosphinine)Mo(CO)(4)(pip) complex 7, which was isolated in 70% yield. In solution, at room temperature for 2 days, 7 transforms into to eta(1)-(five-membered cyclophosphazene)Mo(CO)(5) complex 9 in 45% yield. When 2 equiv of W(CO)(5)(pip) is added to 1, complex 10 featuring a five-membered cyclophosphazene bonded to W(CO)(5)(pip) via a hydrogen bond is isolated in 80% yield. 1,2 lambda(5)-Azaphosphete 2 reacts with piperidine, affording five-membered phosphazene ring 11 in 95% yield, which by subsequent treatment with Mo(CO)(5)(pip) and W(CO)(5)(pip) gives complexes 9 (75% yield) and 10 (83% yield), respectively. Schwartz's reagent reacts with 1, affording five-membered zirconacyclophosphazene 12 in 45% yield. Complexes 4, 7, 10, and 12 are characterized by single-crystal X-ray analyses. These results as a whole demonstrate that in contrast with (E)-phosphazides which behave as four-electron donors via the alpha- and gamma-nitrogen atoms and which are stabilized by complexation, (Z)-phosphazides, such as the 1,2,3,4 lambda(5)-triazaphosphinine 1, act as two-electron donors via the beta-nitrogen atom, and are destabilized by the metal with respect to nitrogen elimination.