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首页> 外文学位 >Solution phase and polymer bound ruthenium carbene complexes for olefin metathesis.
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Solution phase and polymer bound ruthenium carbene complexes for olefin metathesis.

机译：溶液相和聚合物结合的钌卡宾配合物用于烯烃复分解。

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摘要

Several ruthenium carbene complexes have been shown to catalyse olefin metathesis. In this work the ligand environment of Grubbs first generation catalyst was modified in a systematic manner with ligands related Grubbs Schiff base ligand in order to determine the effect of various ligand structural features on carbene stability and catalytic activity. Linker ligands were then synthesized based on promising solution phase ligands. These linker ligands were attached to Merrifield resin and treated with Grubbs first generation catalyst in order to generate polymer bound ruthenium carbene complexes. These polymer bound complexes were then evaluated for catalytic activity and stability. The polymer bound complexes were found to be significantly more thermally stable than the corresponding solution phase complexes.;In the course of this work it was discovered that the carbene moiety of Grubbs first generation catalyst equilibrates with alkenes in the reaction mixture. The equilibrium constants for carbene exchange were determined for several alkenes having a wide range of steric demand. Relative Gibbs free energies of formation were calculated for the resulting carbene complexes. The free energies increased with increasing steric demand of the carbene and spanned 5.6 kcal/mol. This thermodynamic data complements the extensive kinetic data obtained by Grubbs.
机译：几种钌卡宾配合物已显示出催化烯烃复分解的作用。在这项工作中，用与配体相关的Grubbs Schiff碱配体系统地修饰了Grubbs第一代催化剂的配体环境，以确定各种配体结构特征对卡宾稳定性和催化活性的影响。然后基于有前途的溶液相配体合成接头配体。这些接头配体连接到Merrifield树脂上，并用Grubbs第一代催化剂处理，以生成聚合物结合的钌卡宾配合物。然后评估这些聚合物结合的配合物的催化活性和稳定性。发现与聚合物结合的配合物比相应的溶液相配合物具有更高的热稳定性。在这项工作的过程中，发现格拉布斯第一代催化剂的卡宾部分与反应混合物中的烯烃平衡。确定了具有宽范围空间需求的几种烯烃的卡宾交换平衡常数。计算得到的卡宾配合物的相对吉布斯自由形成能。随着卡宾的空间需求增加，自由能增加，跨度为5.6 kcal / mol。该热力学数据补充了格鲁布斯获得的广泛的动力学数据。

著录项

  • 作者

    Lane, David Redick, III.;

  • 作者单位

    University of California, Davis.;

  • 授予单位 University of California, Davis.;
  • 学科 Chemistry Inorganic.;Chemistry Organic.
  • 学位 Ph.D.
  • 年度 2007
  • 页码 370 p.
  • 总页数 370
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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