Chemical and Electrochemical Generation of Novel Anions and Dianions of Arene and Olefincarbonylmetal Complexes. New Organic Synthetic Methodologies

这项有机和大分子化学项目资助了内布拉斯加州大学Reuben Rieke教授的研究，该研究涉及芳烃和芳烃取代烯烃的单羰基和双羰基金属配合物的新化学反应。特别感兴趣的将是分析复杂的阴离子与各种亲电试剂的反应，因为这些具有演变成复杂有机合成有用的新合成方法的潜力。对双配合物的研究将集中在联苯和其他共轭双芳烃体系上。共轭双配合物表现出不同寻常的还原特性，每个三羰基铬单位还原一个电子，生成稳定的离子。与伯卤化物反应，只有邻位产物产率高。将确定这种区域选择性的机制起源，并探讨其在新的合成方法中的应用。还将制备新的芳烃取代烯烃混合金属双配合物体系，该体系在还原后将得到稳定的碘离子。这些离子与亲电试剂的反应为控制分子的芳烃和烯烃部分之间的区域选择性提供了机会。各种电化学和立体化学技术将用于探索这些反应的反应机理。

This grant in the Organic and Macromolecular Chemistry Program supports research of Prof. Reuben Rieke, University of Nebraska, which is concerned with new chemical reactions of mono- and biscarbonylmetal complexes of arenes and arene-substituted olefins. Of particular interest will be analysis of the reactions of the complex dianions with a variety of electrophiles, because these hold the potential for evolving into useful new synthetic methodologies for complex organic synthesis. The studies on bis-complexes will concentrate on biphenyl and other conjugated diarene systems. The conjugated bis-complexes show the unusual reduction characteristics of one electron per chromium tricarbonyl unit, to give stable dianions. Reaction with primary halides gives high yields to only the ortho product. The mechanistic origins of this regioselectivity will be determined and its utility in new synthetic methodologies will be explored. New mixed metal bis-complex systems of arene-substituted olefins will also be prepared, which should lead to stable dianions upon reduction. The reactions of these dianions with electrophiles offer opportunities for control of regioselectivity between the arene and olefin portions of the molecule. A variety of electrochemical and stereochemical techniques will be used to probe the reaction mechanisms of these reactions.