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首页> 外文学位 >Synthetic models for inorganic intermediates in the oxidation of hydrocarbons by high valent vanadium and chromium oxo complexes. Low-coordinate nitrosyl complexes of iron, cobalt and nickel for nitric oxide activation.
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Synthetic models for inorganic intermediates in the oxidation of hydrocarbons by high valent vanadium and chromium oxo complexes. Low-coordinate nitrosyl complexes of iron, cobalt and nickel for nitric oxide activation.

机译：高价钒和铬氧代配合物氧化烃类中无机中间体的合成模型。铁，钴和镍的低配位亚硝酰基配合物，用于一氧化氮活化。

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摘要

We are exploring new transition metal complexes related to the structurally simple chromyl chloride that serve as synthetic models for the inorganic intermediates involved in the oxidation of hydrocarbons by high valent metal-oxo complexes. Our strategy has involved the use of bulky, electron-poor 2,6-diarylylbenzoates as ancillary ligands. The molecular shape provided by the two diarylbenzoate ligands should sterically discourage bridging interactions between metal centers that could lead to oligomerization, enabling the isolation of the reduced metal species and their identification by traditional solution techniques and by X-ray crystallography. We have studied carboxylate complexes of V and Cr as synthetic models for inorganic intermediates in the oxidation of hydrocarbons by high valent, first row transition metal oxo complexes. By using sterically hindered, electron-poor 2,6-diarylbenzoate ligands (ArCEEH, E = O, S), new mono- and dinuclear chromium and vanadium carboxylate complexes were prepared and structurally characterized. We have explored the effect that sterically-hindered, electron-poor 2,6-diarylbenzoates have on the reactivity of d(0), terminal metal-oxo moieties.;Due to the fact that NO is an important signaling molecule in biological systems, the chemistry of transition metal nitrosyl complexes has received increased attention in recent years. Many biomimetic metal nitrosyl complexes of Fe-Cu, both heme analogues as well as non-heme have been synthesized and provide insight into the active sites of such enzymes. There are very few examples of transition metal nitrosyl complexes with a coordination number of three. We aim to sterically protect the metal centers of interest with bulky ligands such as beta-diketiminates, a family of chelating, monoanionic anicilary ligands well-suited for later, first row transition metal chemistry. The recent synthesis in our laboratory of low-valent metal complexes that employ beta-diketiminates as well as a labile ligand sparked our interest to prepare metal nitrosyl complexes. Our goals are to explore the chemistry of NO in well-defined low-coordinate molecular environments to uncover new insights into its reactivity. We have synthesized and characterized mono and dinitrosyl complexes of Fe, Co and Ni and studied their reactivity towards reactions involving the activation of coordinated NO. (Abstract shortened by UMI.)
机译：我们正在探索与结构简单的苯甲酰氯有关的新型过渡金属配合物，这些过渡金属配合物可作为参与高价金属-氧代配合物氧化烃的无机中间体的合成模型。我们的策略涉及使用笨重的电子贫化的2,6-二芳基苯甲酸酯作为辅助配体。由两个二芳基苯甲酸酯配体提供的分子形状应在空间上阻止可能导致低聚的金属中心之间的桥连相互作用，从而能够还原还原的金属物种，并通过传统的溶液技术和X射线晶体学对其进行鉴定。我们已经研究了V和Cr的羧酸盐配合物，作为无机中间体在高价，第一行过渡金属氧代配合物氧化烃中的合成模型。通过使用空间受阻的，贫电子的2,6-二芳基苯甲酸酯配体（ArCEEH，E = O，S），制备了新的单核和双核铬和钒钒羧酸盐配合物，并进行了结构表征。我们已经研究了空间受阻的电子贫乏的2,6-二芳基苯甲酸酯对d（0）末端金属-氧代部分的反应性的影响。由于NO是生物系统中重要的信号分子，近年来，过渡金属亚硝酰基配合物的化学越来越受到关注。 Fe-Cu的许多仿生金属亚硝酰基复合物，血红素类似物和非血红素均已合成，可洞悉此类酶的活性位点。配位数为3的过渡金属亚硝酰基配合物的例子很少。我们的目标是通过庞大的配体（例如β-二酮）（一种非常适合于以后的第一行过渡金属化学反应的螯合单阴离子苯胺配体系列）在空间上保护目标金属中心。我们实验室中最近合成的低价金属配合物，该配合物使用β-二酮和不稳定的配体，激发了我们对制备金属亚硝酰基配合物的兴趣。我们的目标是在定义明确的低配位分子环境中探索NO的化学性质，以发现有关其反应性的新见解。我们已经合成和表征了Fe，Co和Ni的单和二亚硝基配合物，并研究了它们对涉及配位NO活化的反应的反应性。 （摘要由UMI缩短。）

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  • 作者

    Puiu, Simona C.;

  • 作者单位

    Georgetown University.;

  • 授予单位 Georgetown University.;
  • 学科 Chemistry Inorganic.
  • 学位 Ph.D.
  • 年度 2004
  • 页码 187 p.
  • 总页数 187
  • 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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