High Energy Routes to Strained Molecules and Reactive Intermediates

在这个由化学系化学结构、动态和机理B计划资助的项目中，新汉普郡大学化学系的理查德·约翰逊教授和他的学生将研究高能中间体的化学，这些中间体是通过超强酸中的质子化、氢原子加成、热分解或电子转移而产生的。一个重要的目标是探索多环芳烃的阳离子和自由基异构化。从星际化学到分子电子学材料，这些物质在整个科学领域都具有广泛的重要性。这个项目包括理论和实验之间的高度协同。拟议的研究代表了一系列丰富而多样的计算和实验经验，将成为新汉普郡大学研究生和本科生，包括妇女和少数族裔的有效培训。外展活动将侧重于开发新的本科生实验室实验，这些实验基于国家科学基金会资助的整个化学领域的研究。这项拟议的研究延续了之前由NSF资助的研究。重点将放在芳香化合物的重排、环化和偶联反应上。提议的超强酸催化化学将利用微波反应器来扩大阳离子化学的范围，以包括新的更高能量的过程。在最近小组发现的基础上，包括超强酸和自由基催化的多环芳烃骨架异构化，首席研究员和他的学生将把理论和实验结合起来，寻求对这些反应的机理理解。一个重要的目标是证明氢原子在高温化学中是通用的催化剂，就像质子催化溶液中的反应一样。第二个主要重点将是在新汉普郡大学开发的极性双分子反应电子转移模型的方法学开发和新的应用。该模型将所有极性双分子反应视为单电子转移过程，使用自旋密度图成功预测了一系列化学反应中的区域化学和立体化学。

In this project funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Richard Johnson and his students at the University of New Hampshire Department of Chemistry will investigate the chemistry of highly energetic intermediates, which are generated either by protonation in superacids, hydrogen atom addition, thermolysis or electron transfer. One important goal is to explore the cationic and free-radical isomerization of polycyclic aromatic hydrocarbons. These are substances of broad importance across science - from interstellar chemistry to materials for molecular electronics. This project includes a high level of synergy between theory and experiment. The proposed research represents an intellectually rich and diverse series of computational and experimental experiences, which will serve as effective training for graduate and undergraduate students at the University of New Hampshire, including women and minorities. Outreach activities will focus on the development of new undergraduate laboratory experiments which are based on NSF-funded research across the field of chemistry. The proposed research continues previous NSF-funded studies. The major focus will be on rearrangements, cyclizations and coupling reactions of aromatic compounds. Proposed superacid-catalyzed chemistry will utilize a microwave reactor to extend the range of cationic chemistry to include new higher energy processes. Building on recent group discoveries, which include both superacid and free-radical catalyzed skeletal isomerizations of polycyclic aromatic hydrocarbons, the principal investigator and his students will combine theory and experiment to seek mechanistic understanding of these reactions. One important goal is to demonstrate that hydrogen atoms are universal catalysts in high temperature chemistry, just as the proton catalyzes reactions in solution. A second major emphasis will be on methodology development and new applications of the electron transfer model for polar bimolecular reactions which was developed at the University of New Hampshire. This model treats all polar bimolecular reactions as single electron transfer processes, using spin density maps to successfully predict regiochemistry and stereochemistry in a broad array of chemical reactions.