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首页> 外文学位 >Organometallic chemistry of eta(6)-aromatic-cyclic-hydrocarbon manganese tricarbonyl complexes and electrochemical study of (arene)Cr(CO)(3) complexes having a pendent ferrocenyl switch.
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Organometallic chemistry of eta(6)-aromatic-cyclic-hydrocarbon manganese tricarbonyl complexes and electrochemical study of (arene)Cr(CO)(3) complexes having a pendent ferrocenyl switch.

机译：η（6）-芳香族环烃三羰基锰锰配合物的有机金属化学和具有二茂铁基悬垂开关的（arene）Cr（CO）（3）配合物的电化学研究。

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摘要

The important Mn{dollar}rmsp+(CO)sb3{dollar} organometallic moiety can be coordinated in an {dollar}etasp6{dollar}-fashion to aromatic organic ligands by three different methods. These synthetic routes involve a combination of acidic conditions and long reflux times at high temperatures. Thus organic ligands which are not thermally robust or contain acid sensitive functional groups are either difficult to coordinate or are coordinated in low yields and purity. The first part of this thesis focuses on the development of a manganese tricarbonyl transfer reagent which can mildly coordinate the Mn{dollar}rmsp+(CO)sb3{dollar} moiety to a variety of arene organic ligands. The reagent was based on the ring slippage effect, which is well known to occur in organometallic compounds such as (polyarene)Mn{dollar}rmsp+(CO)sb3{dollar}. Kinetic data from a variety of (polyarene)Mn{dollar}rmsp+(CO)sb3{dollar} complexes in a 1.0 M methylene chloride solution of acetonitrile were used to target the most promising compounds. Coordination of several representative arene compounds was then demonstrated under optimized conditions.; The second part of this thesis presents an application of manganese tricarbonyl mediated chemistry. A derivative of the aromatic steroid, 1-methylestrone, was synthesized in overall 43% yield starting with the readily available 3-methoxyestrone. The synthetic procedure involved the protection of the organic functionalities, coordination of the transition metal carbonyl (Mn{dollar}rmsp+(CO)sb3rbrack{dollar}, functionalisation of the arene ring, deprotection of the organic functional groups and final demetalation.; The final part of this thesis explores the electrochemical properties of a series of compounds based on a molecular system having an iron metal center covalently attached to a chromium metal center via an organic linker. Oxidation at the iron metal center (E{dollar}sb{lcub}1/2{rcub}{dollar} = 0.68 V) of the initial compound, {dollar}rm CPFe(Csb5Hsb4Csb6Hsb5)Cr(CO)sb3{dollar} (5-1a), in the presence of P(OEt){dollar}sb3{dollar} effectively induces reaction to occur at the chromium center (E{dollar}sb{lcub}1/2{rcub}{dollar} = 1.07 V), which has a higher oxidation potential than the iron center. Two different products could be detected electrochemically which were confirmed by electrochemical analysis of a genuine sample of each product. The identification allowed for an elaborate reaction pathway scheme to be compiled for (5-1a). Computer simulations of the cyclic-voltammograms were used to predict rate constants and provide theoretical evidence for the proposed pathway. A model was also proposed to try to explain how the induction effect could occur. Furthermore, this model was tested by the electrochemical characterization of several derivatives of (5-1a). By placing various substituents on the organic portions of (5-1a), the potentials could be adjusted so as to tune the reactivity of the system. It was also found that the reactivity could be effected by changing the organic linker. Experimental efforts were also made to try to determine if an intermolecular mechanism could account for the observations.
机译：可以通过三种不同的方法将重要的Mn {dol} rmsp +（CO）sb3 {dol}有机金属部分配位成芳香族有机配体。这些合成途径涉及酸性条件和高温下较长的回流时间。因此，不具有热稳定性或包含酸敏感性官能团的有机配体难以配位或以低产率和纯度配位。本文的第一部分着重于三羰基锰转移试剂的开发，该试剂可以将Mn {dollar} rmsp +（CO）sb3 {dollar}部分适度配位至各种芳烃有机配体。该试剂基于环滑移效应，众所周知，环滑移效应发生在有机金属化合物中，例如（聚芳烃）Mn {美元} rmsp +（CO）sb3 {美元}。在1.0 M的乙腈二氯甲烷溶液中，来自各种（聚芳烃）Mn {dollar} rmsp +（CO）sb3 {dollar}配合物的动力学数据被用于靶向最有前景的化合物。然后在优化条件下证明了几种代表性的芳烃化合物的配位。本文的第二部分介绍了三羰基锰介导的化学的应用。从容易获得的3-甲氧基雌酮开始，以总43％的产率合成了芳香族类固醇的衍生物1-甲基雌酮。合成过程包括有机官能团的保护，羰基过渡金属（Mn {dollar} rmsp +（CO）sb3rbrack {dollar}的配位，芳烃环的官能化，有机官能团的脱保护和最终的脱金属。本文的一部分将探讨一系列基于分子系统的化合物的电化学性质，该分子系统具有通过有机连接剂与铬金属中心共价连接的铁金属中心。在铁金属中心的氧化（E {dollar} sb {lcub}在P（OEt）{美元的存在下}初始化合物{美元} rm CPFe（Csb5Hsb4Csb6Hsb5）Cr（CO）sb3 {美元}（5-1a）的1/2 {rcub} {美元} = 0.68 V） } sb3 {dollar}有效地诱导在铬中心发生反应（E {dollar} sb {lcub} 1/2 {rcub} {dollar} = 1.07 V），该氧化电位比铁中心高。可以通过电化学方法检测到的产品，通过对真实样品的电化学分析得以确认每个产品。通过鉴定，可以为（5-1a）编写详细的反应途径方案。循环伏安图的计算机模拟用于预测速率常数，并为所建议的途径提供理论依据。还提出了一个模型来尝试解释诱导作用如何发生。此外，通过电化学表征（5-1a）的几种衍生物测试了该模型。通过将各种取代基置于（5-1a）的有机部分上，可以调节电势以调节体系的反应性。还发现可以通过改变有机连接基来实现反应性。还进行了实验性尝试，以确定分子间机制是否可以解释这些观察结果。

著录项

  • 作者

    Yeung, Lee Kon.;

  • 作者单位

    Brown University.;

  • 授予单位 Brown University.;
  • 学科 Chemistry Inorganic.; Chemistry Organic.
  • 学位 Ph.D.
  • 年度 1998
  • 页码 246 p.
  • 总页数 246
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 无机化学;有机化学;
  • 关键词

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