Synthetic and Electrochemical Studies of Oganometallics

布朗大学化学系的Dwight a . Sweigart博士受到化学系无机、生物无机和有机金属项目的支持，研究三羰基锰与芳香配体的配位所影响的化学反应，并开发含有氧化还原开关的系统，以激活或关闭远程金属中心。利用三羰基配位锰片段活化芳香配体的能力，可以制备各种单芳烃和杂环化合物。实例包括功能化的中心聚丹烃和立体选择性衍生化的前手性芳烃。芳烃配体交换将扩展到含有多种金属的共轭聚芳烃的双金属配合物。以对苯二酚和儿茶酚配合物为重点，对金属的氧化还原性质进行了评价。这些研究将集中于设计金属-金属相互作用可以通过电化学开关打开或关闭的系统。利用三羰基锰片段的反应性，将开发硫碳键的还原插入反应，重点是与HDN和HDS有关的过程。本项目将重点开发锰金属配合物的几种应用。第一个目标是合成选定类型的有机分子，并利用含有锰的物种来破坏噻吩中的碳硫键。这项研究意义重大，因为噻吩类材料的去除对化石燃料的脱硫非常重要，而锰因其低毒和相对丰度而对这一应用特别有吸引力。另一项主要活动是开发一种系统，在这种系统中，电子向金属原子的转移或从金属原子的转移将控制第二个金属中心的行为。这将涉及到几个领域，包括金属材料的电导率和光学特性的控制。

Dr. Dwight A. Sweigart, Department of Chemistry, Brown University, is supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division for the study of chemical reactions effected by the coordination of the manganese tricarbonyl moiety to aromatic ligands and for the development of systems that contain a redox switch to activate or deactivate remote metal centers. The ability of coordinated manganese tricarbonyl fragments to activate aromatic ligands will be exploited to prepare a wide range of monoarenes and heterocycles. Examples include functionalized centropolyindan hydrocarbons and stereoselectively derivatized prochiral arenes. Arene ligand exchange will be extended to bimetallic complexes of conjugated polyarenes containing a variety of metals. Concentrating on hydroquinone and catechol complexes, the redox properties of the metals will be evaluated. The studies will converge into the design of systems in which metal-metal interactions can be electrochemically switched on or off. Drawing on the reactivity of the manganese tricarbonyl fragment, reductive insertion reactions into sulfur-carbon bonds will be developed, with an emphasis on processes related to HDN and HDS. This project will concentrate on developing several applications for manganese metal complexes. The first of these aims at the synthesis of selected types of organic molecules and at the use of manganese containing species to break carbon-sulfur bonds in thiophenes. This study is significant because the removal of thiophenic materials is important to the desulfurization of fossil fuels and manganese is especially attractive for this application because of its low toxicity and relative abundance. Another major activity is the development of systems in which the transfer of an electron to or from a metal atom will control the behavior of a second metal center. This will have relevance to several areas including the control of conductivity and optical properties in metal containing materials.