The Electrochemical Preparation and Study of Strong Carbon-, Nitrogen-, and Oxygen-Centered Bases

该项目属于分析和表面化学的一般领域，以及有机电化学的子领域。本实验的主要目的是研究溶液中强Bronsted碱的电化学制备，并研究它们的电化学性质及其反应。具体地说，Hawley教授和他的学生将：(1)发展制备弱Bronsted酸共轭碱的电化学方法；(2)测定这些阴离子的氧化还原电位；(3)研究这些阴离子与非电活性底物的反应；(4)测定两元Bronsted酸的去质子化反应的区域选择性以及区域异构体的异构化动力学；(5)考察与两亲电生碱的质子化有关的区域选择性；和(6)探索产生超催化活性的电生碱的制备。这些研究对我们了解自由基离子和相关物种的热力学性质和反应动力学是重要的，这导致了电子转移一般理论的发展和完善。此外，霍利教授的研究应该对有机化学的继续发展和增加我们对许多在新材料合成中极其有用的反应的理解具有重要意义。

This project is in the general area of analytical and surface chemistry and in the subfield of organic electrochemistry. The thrust of this experimental program is to investigate the electrochemical preparation of strong Bronsted bases in solution and to study their electrochemical properties and their reactions. Specifically, Professor Hawley and his students will (1) develop electrochemical methods for the preparation of the conjugate bases of weak Bronsted acids; (2) determine the redox potentials of these anions; (3) study the reactions of these anions with electroinactive substrates; (4) determine the regioselectivity of deprotonation of ambident Bronsted acids as well as the kinetics of isomerization of the regioisomers; (5) examine the regioselectivity associated with protonation of the ambident electrogenerated bases; and (6) explore the preparation of electrogenerated bases that give rise to hypercatalytic activity. These studies are important to our knowledge of the thermodynamic properties and reaction kinetics of radical ions and related species that lead to the development and refinement of general theories of electron transfer. Additionally, Professor Hawley's studies should be of importance to the continued development of organic chemistry and in increasing our understanding of many reactions that are extremely useful in the synthesis of new materials.