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首页> 外文学位 >Redox and Coordination Chemistry of Bis-Bidentate Para-Hydroquinones.
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Redox and Coordination Chemistry of Bis-Bidentate Para-Hydroquinones.

机译：双齿对氢醌的氧化还原和配位化学。

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摘要

The chemistry of a series of para-hydroquinones substituted in the 2,5-positions with a proton accepting amine group has been investigated. The p-hydroquinones are designed with bis-bidentate coordination pockets allowing for the bridging of two metals and extended multimetallic complexes. Several aspects of the hydroquinones chemistry was examined, including the redox behaviour and properties of the hydroquinones while in their free forms, complexed to palladium and complexed to boron.;The redox properties of para-hydroquinones which contain intramolecular hydrogen bonds as indicated by X-ray structural and spectroscopic data were examined. The cyclic voltammograms of some of these hydroquinones indicated they could be oxidized reversibly to give dicationic benzoquinones. The oxidized forms have been chemically isolated and characterized for the first time. Characterization data of the dicationic benzoquinones revealed the OH protons are transferred intramolecularly to the adjacent nitrogen bases. Spectroscopic solution data for the p-benzoquinone dications suggests that the intramolecular hydrogen bonds in the redox related p-hydroquinone are no longer present. A correlation between the oxidation potential of the 2,5-substituted-p-hydroquinone and base strength of the nitrogen substituent was shown to exist.;The bis-bidentate p-hydroquinones were coordinated to palladium resulting in dinuclear complexes. The non-innocence of the ligand was preserved upon coordination but the complexes are oxidized at more positive potentials in comparison to the analogous p-benzoquinone species. Two of the palladium complexes were chemically oxidized resulting in the semiquinone radical redox state of the ligand. The EPR and UV-vis spectroscopy of the radical p-semiquinone palladium complexes indicates their properties are similar to o-semiquinone palladium complexes.;The bis-bidentate p-hydroquinones and some related ligands were also coordinated to the main group element, boron. Cyclic voltammetry of the boron complexes revealed the redox properties of the bridging p-hydroquinone were perturbed and redox processes occurred at even more positive potentials in comparison to the analogous palladium complexes. The dinuclear boron complexes were highly fluorescent with quantum yields calculated to be in the range of 0.36--0.52. These boron complexes incorporated an uncommon ancillary ligand, acetate. The acetate ligand was found to be advantageous for the solubility and fluorescence properties for one of the boron compounds in comparison to the analogous boron complex incorporating the more commonly used fluorine ancillary ligand.
机译：已经研究了在2,5位上被质子接受胺基取代的一系列对氢醌的化学反应。对苯二酚设计有双齿配位口袋，可以桥接两种金属和扩展的多金属配合物。检查了对苯二酚化学的几个方面，包括对苯二酚的游离态，与钯络合和与硼络合的氧化还原行为和氢醌的性质。检查了射线结构和光谱数据。其中一些对苯二酚的循环伏安图表明，它们可以被可逆氧化，得到顺式苯醌。氧化形式已被化学分离并首次表征。指示性苯醌的表征数据表明，OH质子在分子内转移至相邻的氮碱基。对苯二酚指示的光谱解决方案数据表明，氧化还原相关的对氢醌中不再存在分子内氢键。表明2,5-取代的对氢醌的氧化电势与氮取代基的碱强度之间存在相关性。双齿双对氢醌与钯配位，生成双核络合物。配体的非纯性在配位时得以保留，但是与类似的对苯醌类相比，络合物在更正的电位上被氧化。两个钯配合物被化学氧化，形成配体的半醌自由基氧化还原态。自由基对半醌钯配合物的EPR和紫外可见光谱表明，它们的性质与邻半醌钯配合物相似。硼配合物的循环伏安法表明，与类似的钯配合物相比，桥联对氢醌的氧化还原特性受到干扰，并且氧化还原过程在甚至更高的正电势下发生。双核硼配合物是高度荧光的，其量子产率经计算为0.36--0.52。这些硼配合物掺入了罕见的辅助配体乙酸盐。与结合了更常用的氟辅助配体的类似硼配合物相比，发现乙酸酯配体对于一种硼化合物的溶解度和荧光性质是有利的。

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  • 作者

    Trefz, Tyler.;

  • 作者单位

    University of Victoria (Canada).;

  • 授予单位 University of Victoria (Canada).;
  • 学科 Inorganic chemistry.;Organic chemistry.
  • 学位 Ph.D.
  • 年度 2013
  • 页码 264 p.
  • 总页数 264
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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