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Synthesis, structures, and reactivity of biologically relevant sulfur-containing copper(i) complexes.

机译：生物学相关的含硫铜（i）配合物的合成，结构和反应性。

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摘要

Several aspects of the bioinorganic chemistry of copper remain elusive. Low-coordinate, sulfur-containing copper sites appear to play different, yet very important roles in biology. These motifs are not well understood, but are implicated in biological copper sequestration, copper transfer, and are found as part of an active site within a particular metalloenzyme system that catalyzes water-gas shift chemistry. The work described in this dissertation details the exploratory synthesis aimed at modeling these systems.;Synthetic efforts to gain access to two-coordinate copper(I) bis(thiolato) species which model copper metallochaperones and metalloregulatory proteins are outlined in Chapter 1. To this end, the synthetic preparation of a new, bulky thiolate ligand precursor, 1-(thioacetyl)triptycene, was devised. Upon deprotection to form 1-(thiolato)triptycene, this ligand affords several new low-coordinate cuprous thiolate complexes. One particular species, [Bu 4N][Cu(STrip)2], exists as an analogue of the copper metallochaperones and metalloregulatory proteins described previously. A cyclic hexameric species, [Bu4N][(CuSTrip)6(mu6-Br)], emerged from the coordination chemistry and features a new cuprous thiolate structure type. Additionally, a few organometallic copper(I) complexes bearing the triptycene ligand are discussed.;Chapter 2 describes the synthesis of new, potentially useful two- and four-coordinate copper(I) silylthiolate complexes and cuprous metallothiols. Here, synthesis and characterization of [Cu(IPr)(SH)] represents the first example of a two-coordinate copper metallothiol species is reported. The reactivity of both copper(I) silylthiolates and cuprous metallothiols was explored within the context of their potential use as starting materials in an effort to construct heteronuclear species.;Chapter 3 details the synthetic efforts toward assembling a structural analogue of the metalloenzyme active site of molybdenum-dependent carbon monoxide dehydrogenase (Mo-CODH). Two synthetic methodologies, silane-mediated coupling and the reaction of terminal sulfido molybdenum species with labile copper(I) salts, were explored in this context. Several new heteronuclear cluster species containing [Mo(mu-S)2Cu] rhomb core units were formed from the reactions outlined in this chapter. Conclusions are discussed with regard to the synthetic nuances associated with generating a synthetic analogue of the active site of Mo-CODH.;Multinuclear copper species bearing diamino-dithiolate (N2S 2) ligands which formed either serendipitously via ligand exchange or by deliberate syntheses are described in Chapter 4. Copper complexes containing N2S2 ligands appear to stabilize or support mixed-valence cores and can access a variety of structure types. The interesting features associated with these structures are discussed and comments regarding the potential reactivity of these species are framed within a bioinorganic context.
机译：铜的生物无机化学的几个方面仍然难以捉摸。低配位的含硫铜位点似乎在生物学中起着不同但非常重要的作用。这些基序还没有被很好地理解，但是与生物固铜，铜转移有关，并且被发现是催化水煤气变换化学反应的特定金属酶系统中活性位点的一部分。本论文中描述的工作详述了针对这些系统建模的探索性合成。第1章概述了为模拟铜金属伴侣酮和金属调控蛋白的二配位铜（I）双（硫代）物种的合成努力。最后，设计了一种新的大体积硫醇盐配体前体1-（硫代乙酰基）三茂烯的合成制剂。脱保护形成1-（硫醇基）三茂碳烯后，该配体提供了几种新的低配位硫醇亚铜亚铜络合物。一种特定的物种，[Bu 4N] [Cu（STrip）2]，作为前述金属铜伴侣蛋白和金属调控蛋白的类似物存在。环状六聚体[Bu4N] [（CuSTrip）6（mu6-Br）]从配位化学中出现，具有新的硫醇亚铜结构类型。此外，还讨论了一些带有三茂金属配体的有机金属铜（I）配合物。第二章介绍了新的，潜在有用的二和四配位的甲硅烷基硫醇铜（I）配合物和金属硫醇亚铜的合成。在此，报道了[Cu（IPr）（SH）]的合成和表征，该化合物代表了两个配位的铜金属硫醇物种的第一个例子。在其可能用作构建异核物种的起始原料的背景下，探讨了甲硫醇铜（I）和金属硫醇亚铜的反应性;第3章详细介绍了组装金属硫醇活性位点结构类似物的合成工作。钼依赖性一氧化碳脱氢酶（Mo-CODH）。在这种情况下，探讨了两种合成方法，即硅烷介导的偶联以及末端硫基钼物种与不稳定的铜（I）盐的反应。从本章概述的反应中，形成了几种含有[Mo（mu-S）2Cu]菱形核单元的新型异核簇物种。讨论了与产生Mo-CODH活性位点的合成类似物有关的合成细微差别的结论。描述了带有二氨基二硫代盐（N2S 2）配体的多核铜物质，该配体是通过配体交换或通过有意合成而偶然形成的包含N2S2配体的铜络合物似乎可以稳定或支撑混合价核，并且可以使用各种结构类型。讨论了与这些结构相关的有趣特征，并在生物无机环境中对有关这些物种潜在反应性的评论进行了阐述。

著录项

  • 作者

    Ferrara, Skylar J.;

  • 作者单位

    Tulane University School of Science and Engineering.;

  • 授予单位 Tulane University School of Science and Engineering.;
  • 学科 Chemistry Organic.;Chemistry Inorganic.;Chemistry Biochemistry.;Chemistry Molecular.
  • 学位 Ph.D.
  • 年度 2014
  • 页码 449 p.
  • 总页数 449
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 物理化学（理论化学）、化学物理学;
  • 关键词

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