• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文学位 >The development of new routes to half-sandwich metallatricarbadecaborane complexes, triflate-functionalized polyboranes and carboranes, and ammonia borane hydrogen release.
【24h】

The development of new routes to half-sandwich metallatricarbadecaborane complexes, triflate-functionalized polyboranes and carboranes, and ammonia borane hydrogen release.

机译：开发了将半夹心金属三碳杂硼烷络合物，三氟甲磺酸酯官能化的聚硼烷和碳硼烷以及氨硼烷氢释放的新途径。

获取原文
获取原文并翻译 | 示例
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

The three main goals of the research discussed in this dissertation were (1) to expand and characterize the first extensive series of half-sandwich metallatricarbadecaborane complexes, (2) to synthesize and explore the reactivity of 5-TfO-B10H13, and (3) to investigate metal-catalyzed hydrogen release from ammonia borane in ionic liquids. The major achievements are outlined below. Chapter 1 describes the synthesis and structural characterization of the first series of group 9 tricarbadecaboranyl half-sandwich complexes. The tricarbadecaboranyl ligands in these complexes exhibit properties distinct from their cyclopentadienyl analogs, including (1) strong electron-withdrawing properties, (2) the ability to readily form slipped-cage structures, and (3) the ability to stabilize lower metal oxidation states. The unique properties of these complexes mean they could find potential applications as, for example, catalysts for alkyne oligomerizations, polymer and dendrimer building blocks, and synthetic precursors for medicinal therapies. Chapter 2 discusses the development of several high yield pathways to 5-TfO-B10H13. The new routes to 5-TfO-B10H13 allowed for a systematic exploration of its reactivity and potential use as a starting material for the syntheses of other important polyboranes. The combined reactions of the synthesis of 5-TfO-B10H13, the formation of its Lewis acid-base adduct, 5-TfO-6,9-(Me2S)2-B10H11, and the alkyne-insertion and base-promoted cage closure reactions of 5-TfO-6,9-(Me2S)2-B10H11, now provide the first pathways to B-triflate-substituted ortho-carboranes and decaborates. Chapter 3 reports that the metal-catalyzed hydrogen release from ammonia borane (AB) in an ionic liquid produces a significant increase in initial H2-release. However, the metal-catalysts affect only the rate of loss of the first H2-equivalent, with the uncatalyzed and catalyzed rates becoming equal following that point. NMR studies indicate that the mechanism of AB H2-release of these metal-catalyzed systems in ionic liquids appears to be similar to that observed in organic solvents, but differs from that observed in only ionic liquids.
机译：本文讨论的研究的三个主要目标是（1）扩展和表征第一个广泛的半夹心金属三碳碳硼烷复合物系列；（2）合成和探索5-TfO-B10H13的反应性；以及（3）研究离子液体中氨硼烷中金属催化的氢释放。主要成就概述如下。第1章描述了第9族三碳杂硼烷基半三明治复合物的第一系列的合成和结构表征。这些配合物中的三碳硼烷硼烷基配体表现出不同于其环戊二烯基类似物的特性，包括（1）强大的吸电子特性，（2）易于形成滑笼结构的能力，以及（3）稳定较低的金属氧化态的能力。这些复合物的独特性质意味着它们可以找到潜在的应用，例如，用于炔烃低聚的催化剂，聚合物和树枝状聚合物的结构单元以及用于药物治疗的合成前体。第2章讨论了通往5-TfO-B10H13的几种高产途径的发展。通往5-TfO-B10H13的新路线允许对其活性进行系统的探索，并有可能用作其他重要聚硼烷的合成原料。 5-TfO-B10H13的合成，其路易斯酸碱加合物，5-TfO-6,9-（Me2S）2-B10H11的合成，炔烃插入和碱促进的笼封闭反应的组合反应5-TfO-6,9-（Me2S）2-B10H11的合成，现在提供了通往B-三氟甲磺酸盐取代的邻氨基甲酸酯和十硼酸盐的第一条途径。第3章报告说，离子液体中金属硼烷（AB）中金属催化的氢释放会导致初始H2释放显着增加。但是，金属催化剂仅影响第一H2当量的损失速率，此后未催化和催化速率相等。 NMR研究表明，离子液体中这些金属催化体系的AB H2释放机理似乎与有机溶剂中观察到的机理相似，但与仅离子液体中观察到的机理不同。

著录项

  • 作者

    Berkeley, Emily Robyn.;

  • 作者单位

    University of Pennsylvania.;

  • 授予单位 University of Pennsylvania.;
  • 学科 Chemistry General.;Chemistry Inorganic.
  • 学位 Ph.D.
  • 年度 2013
  • 页码 371 p.
  • 总页数 371
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号