Physical and Synthetic Studies of Organometallic Electrophiles

在布朗大学无机、生物无机和有机金属化学专业的这个项目中，德怀特·a·斯威加特将研究有机金属化合物的一些反应，其具体目标是：(1)开发新的合成重要有机分子的途径；(2)探索亲电-亲核试剂组合的详细机理途径，从而使预测pi-烃活化成为可能；(3)通过使用低温伏安法和稳态超微电极技术确定电化学检测这些反应的可行性。机理研究一般适用于酸碱反应，并且在可能发现这种反应的普遍亲核反应性尺度方面，可能具有远远超出有机金属化学的理论结果。开创性的实验和理论应用的超微电极提出，应该有助于使这种方法可用于所有化学家。研究了锰、铁、铼、钨的亲电有机金属配合物与芳烃、烯烃、炔等配位的配合物的反应。主要反应是亲核试剂（含碳、氮、磷或氢给体原子）攻击活化的pi-烃，产生功能化分子。提出的研究将为二取代的顺式和反式环己二烯以及新的内功能化环己二烯配合物提供一般途径。

In this project within the Inorganic, Bioinorganic and Organometallic Chemistry Program, Dwight A. Sweigart of Brown University will investigate some reactions of organometallic compounds with the specific goals of (1) developing new synthetic routes to important organic molecules, (2) probing the detailed mechanistic pathways for electrophile-nucleophile combinations so that predictions of pi-hydrocarbon activation become possible, and (3) determining the feasibility of examining these reactions electrochemically by using low temperature voltammetric and steady-state ultramicroelectrode techniques. The mechanistic studies are applicable to acid-base reactions in general and may have theoretical consequences well beyond organometallic chemistry in the possible discovery of an universal nucleophilic reactivity scale for such reactions. Pioneering experimental and theoretical applications of ultramicroelectrodes are proposed that should aid in making this methodology available to all chemists. The reactions of electrophilic organometallic complexes of manganese, iron, rhenium and tungsten containing coordinated pi-hydrocarbons such as arenes, alkenes and alkynes will be examined. The primary reaction is attack by nucleophiles (with carbon, nitrogen, phosphorus or hydrogen donor atoms) at the activated pi-hydrocarbon to produce functionalized molecules. The proposed study will provide general routes to disubstituted cis- and trans-cyclohexadienes as well as novel endofunctionalized cyclohexadienyl complexes.