High Energy Routes to Strained Molecules and Reactive Intermediates

应变分子和反应性中间体的高能路线

• 批准号: 1362519
• 负责人: Arthur Greenberg
• 金额: $ 53.5万
• 依托单位: University of New Hampshire
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2014
• 资助国家: 美国
• 起止时间: 2014-08-01 至 2020-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1362519&HistoricalAwards=false
• 关键词: Energy; Routes; Strained; Molecules; Reactive

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.

在这个由化学系的化学结构，动力学机制B计划资助的项目中，新罕布什尔州大学化学系的Richard约翰逊教授和他的学生将研究高能中间体的化学，这些中间体是由超强酸中的质子化，氢原子加成，热交换或电子转移产生的。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。 这些物质在科学上具有广泛的重要性-从星际化学到分子电子材料。该项目包括理论和实验之间的高度协同作用。 拟议的研究代表了一系列智力丰富和多样化的计算和实验经验，这将作为有效的培训研究生和本科生在新罕布什尔州，包括妇女和少数民族的大学。外联活动将侧重于开发新的本科实验室实验，这些实验基于NSF资助的化学领域研究。这项研究延续了之前NSF资助的研究。重点将放在芳族化合物的重排、环化和偶联反应上。提出的超强酸催化化学将利用微波反应器来扩展阳离子化学的范围，以包括新的更高能量的过程。 基于最近的小组发现，其中包括多环芳烃的超强酸和自由基催化的骨架异构化，首席研究员和他的学生将联合收割机理论和实验相结合，以寻求这些反应的机理理解。 一个重要的目标是证明氢原子是高温化学中的通用催化剂，就像质子催化溶液中的反应一样。 第二个主要重点将是极性双分子反应的电子转移模型，这是在新罕布什尔州大学开发的方法的发展和新的应用。 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地预测了广泛的化学反应中的区域化学和立体化学。