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首页> 外文学位 >Synthesis, characterization and bioinspired reactivity of metal complexes by fluorinated hydrotrispyrazolylborate and dihydrobispyrazolylborate ligands.
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Synthesis, characterization and bioinspired reactivity of metal complexes by fluorinated hydrotrispyrazolylborate and dihydrobispyrazolylborate ligands.

机译：氟化氢三吡唑基硼酸酯和二氢双吡唑基硼酸酯配体的金属配合物的合成，表征和生物启发性。

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摘要

Using fluorinated hydrotrispyrazolylborate (Tp) ligand, we have synthesized a series of copper(I) complexes, including a copper(I) dimer (with TpCF3,CH3) and the first structurally characterized mononuclear copper(I)-acetone complex (with TpCF3,CF3). Bioinspired reactivity of CH2Cl2 solution of both complexes towards dioxygen and ethylene has been studied. The first room-temperature reversible oxygen binding was achieved by the copper-TpCF3,CH3 system, which behaved as a functional model for hemocyanin (Hc). The dicopper(II) side-on (or μ-η2:η2) peroxo complexes with TpCF3,CH3 and TpCF3,CF3 were isolated as unusual room-temperature stable solid, and fully characterized. Resonance Raman data showed increased fluorination of Tp ligand resulted in stronger O-O bond in these dicopper(II) peroxo complexes. Two stable copper(I)-ethylene complexes were synthesized as the models for the ethylene-binding sites in plants. Fluorination on Tp ligand increases the σ-donation from ethylene to copper(I), but decreases the π-backdonation from copper(I) to ethylene. Since σ-donation is dominant in copper(I)-ethylene complexes, copper(I) fluorinated-Tp ethylene complexes are more stable than the nonfluorinated analog.; Manganese and cobalt complexes with fluorinated Tp ligands were synthesized and compared with their nonfluorinated analog. Some copper complexes with fluorinated dihydrobispyrazolylborate (Bp) ligands were synthesized and characterized, including a copper(I)-cyclohexene complex with BpCF3,CF3 ligand.
机译：使用氟化的氢三吡唑基硼酸酯（Tp）配体，我们合成了一系列铜（I）配合物，包括铜（I）二聚体（具有Tp CF3，CH3 ）和第一个结构上表征的单核铜（I ）-丙酮配合物（与Tp CF3，CF3 ）。研究了两种配合物的CH 2 Cl 2 溶液对双氧和乙烯的生物反应性。铜-Tp CF3，CH3 系统实现了第一个室温可逆氧结合，该系统可作为血红蛋白（Hc）的功能模型。具有Tp CF3，CH3 和Tp 2 ：η 2 ）过氧配合物> CF3，CF3 被分离为异常的室温稳定固体，并进行了充分表征。共振拉曼数据显示，Tp配体的氟化作用增加，导致这些dicopper（II）过氧配合物中的O-O键更牢固。合成了两种稳定的铜（I）-乙烯配合物，作为植物中乙烯结合位点的模型。 Tp配体上的氟化作用会增加从乙烯到铜（I）的σ-给体，但会减少从铜（I）到乙烯的π-给体。因为在铜（I）-乙烯络合物中σ-给定占主导地位，所以氟化铜-Tp乙烯铜络合物比非氟化类似物更稳定。合成了具有氟化Tp配体的锰和钴配合物，并与它们的非氟化类似物进行了比较。合成并表征了一些具有氟化二氢双吡唑基硼酸酯（Bp）配体的铜配合物，包括具有BpsuperCF3，CF3 配体的铜（I）-环己烯配合物。

著录项

  • 作者

    Hu, Zhengbo.;

  • 作者单位

    Brown University.;

  • 授予单位 Brown University.;
  • 学科 Chemistry Inorganic.
  • 学位 Ph.D.
  • 年度 2001
  • 页码 283 p.
  • 总页数 283
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 无机化学;
  • 关键词

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