(η5-C5H5)Zr(Cl)[CH=CD((13)CH3)] | 412049-93-5

• 英文名称: (η5-C5H5)Zr(Cl)[CH=CD((13)CH3)]
• CAS: 412049-93-5
• 化学式: C₁₃H₁₅ClZr
• 分子量: 299.92
• InChiKey: KULQQOWXYPVWDS-LPVSFHCCSA-M

计算性质

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

• 作为产物：
  描述：

  乙炔钠 、 碘甲烷-13C 、 [Cp2ZrD(Cl)]n 以 四氢呋喃 为溶剂， 生成 (η5-C5H5)Zr(Cl)[CH=CD((13)CH3)]
  参考文献：
  名称：

  Chain Epimerization during Propylene Polymerization with Metallocene Catalysts:  Mechanistic Studies Using a Doubly Labeled Propylene

  摘要：

  The mechanisms of chain epimerization during propylene polymerization with methylaluminoxane-activated rac-(EBTHI)ZrCl2 and rac-(EBI)ZrCl2 catalysts (EBTHI = ethylenebis(eta(5)-tetrahydroindenyl); EBI = ethylenebis(eta(5)-indenyl)) have been studied using specifically isotopically labeled propylene: CH2=(CDCH3)-C-13. These isospecific catalysts provide predominantly the expected [mmmm] pentads with [-(CH2CDCH3-)-C-13] repeating units (C-13 NMR). Under relatively low propylene concentrations at 50 and 75 degreesC, where stereoerrors attributable to chain epimerization are prevalent, 13C NMR spectra reveal C-13-labeled methylene groups along the polymer main chain, together with [(CDCH3)-C-13] units in [mmmr], [mmrr], and [mrrm] pentads and [(CHCH3)-C-13] units in [mmmmmm] and [mmmmmr] heptads, as well as [mrrm] pentads. The isotopomeric reglomisplacements; and stereoerrors are consistent with a mechanism involving beta-D elimination, olefin rotation and enantiofacial interconversions, and insertion to a tertiary alkyl intermediate [Zr-C(CH2D)((CH3)-C-13)P] (P = polymer chain), followed by the reverse steps to yield two stereoisomers of [Zr-CHDCH((CH3)-C-13)P] and [Zr-(CH2CH)-C-13(CH2D)P], as well as unrearranged [Zr-CH2CD((CH3)-C-13)P]. The absence of observable [-(CH2CHCH2D)-C-13-] in the [mrrm] pentad region of the C-13 NMR spectra provides evidence that an allyl/clihydrogen complex does not mediate chain epimerization.

  DOI：

  10.1021/ja0123296