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首页> 外文学位 >Multidentate PCsp3P-type ligands with engineered avenues for metal-ligand cooperation and their iridium complexes.
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Multidentate PCsp3P-type ligands with engineered avenues for metal-ligand cooperation and their iridium complexes.

机译：具有金属-配体合作的工程途径的多齿PCsp3P型配体及其铱络合物。

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摘要

Phosphine-chelated iridium complexes have been long known to exhibit unique reactivity with respect to bond activation and molecular manipulation. Our attempt is to engineer phosphine-chelated iridium catalytic systems which allow for heightened reactivity and specific selectivity with a focus on bond activation allowing for the functionalization of small molecules. The activation of inert small molecules such as methane or carbon dioxide is inherently difficu however, essential for continued improvements in the utilization of large chemical "feedstocks" such as natural gas. Transition-metal mediated processes provide a pathway for the conversion of these "feedstocks" as liquid fuels or fine chemical precursors. New avenues for activation are needed to increase the potency and selectivity of catalytic transformations.;With this intention, a novel synthetic approach to a series of PC sp3P-type scaffold ligands has been developed in which ancillary positions have been modified in an attempt to promote metal-ligand cooperative ability. The full synthesis and characterization of the ligands PCAnisP, PCPhOHP, and PCTolP as well as their C-H activated iridium complexes, and various substituted complexes will be discussed along with their subsequent reactivity. The robust complexes have shown their propensity for hemilability, aryl and alkyl intermolecular and intramolecular activation, alkane transfer dehydrogenation, unique coordination geometries, and heterolytic cleavage. The presented work represents a series of organometallic complexes that exhibit unique secondary ligand interactions which directly affect their resulting reactivity.
机译：膦螯合的铱络合物早就对键激活和分子操纵表现出独特的反应性。我们的尝试是设计膦螯合的铱催化系统，该系统可提高反应性和比选择性，并着重于键活化以实现小分子的功能化。惰性小分子（例如甲烷或二氧化碳）的活化本来就很困难。但是，这对于持续改进大型化学“原料”（例如天然气）的利用至关重要。过渡金属介导的过程为这些“原料”作为液体燃料或精细化学前体的转化提供了途径。需要新的活化途径来提高催化转化的效力和选择性。基于此意图，已开发出一系列PC sp3P型支架配体的新颖合成方法，其中修饰了辅助位置以试图促进金属-配体的合作能力。配体PCAnisP，PCPhOHP和PCTolP以及它们的C-H活化铱配合物以及各种取代的配合物的完整合成和表征，以及随后的反应性都将进行讨论。坚固的配合物已显示出它们具有半可适应性，芳基和烷基分子间和分子内活化，烷烃转移脱氢，独特的配位几何形状以及杂化裂解的倾向。提出的工作代表了一系列有机金属配合物，这些配合物表现出独特的二级配体相互作用，直接影响其最终反应性。

著录项

  • 作者

    Babbini, Dominic Christopher.;

  • 作者单位

    University of Notre Dame.;

  • 授予单位 University of Notre Dame.;
  • 学科 Inorganic chemistry.;Analytical chemistry.
  • 学位 Ph.D.
  • 年度 2016
  • 页码 247 p.
  • 总页数 247
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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