Synthetic and Electrochemical Studies of Oganometallics

布朗大学化学系的Dwight A.Sweigart博士得到了化学部无机、生物无机和有机金属计划的支持，该计划的目的是研究三甲基锰与芳香族配体配位所影响的化学反应，并开发包含氧化还原开关的系统，以激活或停用远程金属中心。利用配位的三羰基锰片段活化芳香族配体的能力将被用来制备广泛的单芳烃和杂环化合物。例子包括官能化的中心多吲烷烃和立体选择性衍生的前手性芳烃。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络合物。集中于对苯二酚和邻苯二酚络合物，将评估这些金属的氧化还原性能。这些研究将集中在金属-金属相互作用可以电化学开启或关闭的系统设计上。利用锰三羰基片段的反应性，将开发硫-碳键的还原插入反应，重点是与HDN和HDS相关的过程。该项目将专注于开发锰金属络合物的几种应用。第一个目标是合成选定类型的有机分子，并利用含锰物种来破坏噻吩类化合物中的碳-硫键。这项研究具有重要意义，因为脱除含硫物质对化石燃料的脱硫很重要，而锰的低毒和相对丰度对这一应用特别有吸引力。另一个主要活动是发展这样的系统，在该系统中，电子从金属原子转移到金属原子或从金属原子转移将控制第二金属中心的行为。这将与几个领域有关，包括对含金属材料的导电性和光学性质的控制。

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.