Carbanion, Carbocation, Carbenic, and Electron Transfer Initiated Mechanistic Studies

这笔拨款将为圣母大学Xavier Creary教授正在进行的研究项目提供支持。动力学、同位素效应和产物研究将用于阐明有机反应的机制和表征反应中间体。将研究二卤二氮嘧啶，以便为二氮基阴离子中间体的形成提供证据。将探讨在溶剂分解条件下协调循环消除烯烃产品的可能性。还将合成硅基取代的碳烯，并测定硅的迁移倾向。将会确定将含碳分子转化为新的、有趣的分子的几个重要反应的细节。在这些重要的转化中，建议的反应中间体的独立合成将为它们的参与提供明确的证据。电子的转移是否会引发其中一些转变，将通过对反应混合物的仔细分析来检验。预计本研究结果将为预测许多反应的结果提供基础。

This grant will provide support for the ongoing research program of Professor Xavier Creary at the University of Notre Dame. Kinetics, isotope effects, and product studies will be used to elucidate the mechanisms of organic reactions and to characterize reactive intermediates. Dihalodiazirines will be studied in order to provide evidence for the formation of a diaziryl anion intermediate. The possibility of a concerted cyclic elimination to give olefinic products under solvolysis conditions will be explored. Silyl substituted carbenes will also be synthesized and the migratory aptitude of silicon determined. %%% The intimate details of several important reactions that transform carbon containing molecules into new and interesting molecules will be determined. Independent synthesis of the suggested reaction intermediates in these important transformations will allow unambiguous evidence for their involvement. The possibility that the transfer of an electron will trigger some of these transformations will be examined by careful analysis of the reaction mixtures. It is anticipated that the results of this study will provide the basis for predicting the outcome of many reactions.