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

芳烃和烯烃羰基金属配合物的新型阴离子和二价阴离子的化学和电化学生成。

基本信息

批准号：
8719728
负责人：
Reuben Rieke
金额：
$ 24.74万
依托单位：
University of Nebraska-Lincoln
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
1988
资助国家：
美国
起止时间：
1988-02-01 至 1991-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=8719728&HistoricalAwards=false
关键词：
Chemical Electrochemical Generation Novel Anions

项目摘要

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.

有机和高分子化学项目的资助支持Reuben Rieke教授的研究，内布拉斯加州，它关注的是新的化学反应，芳烃的单和双羰基金属络合物，芳烃取代的烯烃。特别令人感兴趣的是分析了络合阴离子与各种亲电体，因为它们具有发展成为有用的新的合成方法，有机合成双配合物的研究主要集中在联苯和其它共轭二芳烃体系。共轭双配合物显示出不寻常的还原特性，三羰基铬单元，得到稳定的二价阴离子。反应与伯卤化物得到高产率，只有邻产品这种区域选择性的机械起源将及其在新合成方法学中的效用将被探索。新的混合金属双配合物体系还将制备芳烃取代的烯烃，其应在还原时导致稳定二价阴离子。这些反应二价阴离子与亲电试剂提供了控制的芳烃和烯烃部分之间的区域选择性分子。各种电化学和立体化学技术将被用来探测的反应机制，这些反应。