Studies of Ionic Pericyclic Reactions in the Gas Phase

气相离子周环反应的研究

• 批准号: 0137627
• 负责人: Paul Wenthold
• 金额: $ 27万
• 依托单位: Purdue University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2002
• 资助国家: 美国
• 起止时间: 2002-06-01 至 2005-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0137627&HistoricalAwards=false
• 关键词: Studies; Ionic; Pericyclic; Reactions; Gas

With the support of the Organic Dynamics Program in the Chemistry Division, Professor Paul Wenthold, of the Department of Chemistry at Purdue University, will investigate pericyclic reactions of ions using flowing afterglow/photoelectron spectroscopy. Among the reactions examined are radical cationic and radical anionic Cope and Diels-Alder reactions. The goal of the work will be to determine the products of the reaction, the mechanism by which they are formed, and the catalytic role of ionization. Solvated ions will be used to probe the role of solvent in determining reaction products. The proposal outlines an extensive program of experimentation to characterize the structure and reactivities of various ion radicals and related novel species, using the specialized capabilities of advanced flowing afterglow instrumentation and a negative ion photoelectron spectrometer now under construction at Purdue. While theory-based calculations will play a role, the main emphasis is clearly on defining structures and patterns of reactivity experimentally. The proposal rests on the curiosity of a mechanistically concerned physical organic chemist fully equipped with the more specialized technical repertoire of an experienced gas-phase ion chemist. Much new information and non-trivial conceptual advances should be gained. Professor Paul Wenthold, of the Department of Chemistry at the Purdue University, with the support of the Organic Dynamics Program, will also continue to train students who will become an integral part of the research and publications resulting from the work. The research results will provide a fresh understanding of novel structures and chemical transformations while demonstrating new applications of emerging technical/instrumental capabilities.

在化学系有机动力学项目的支持下，普渡大学化学系的 Paul Wenthold 教授将利用流动余辉/光电子能谱研究离子的周环反应。研究的反应包括自由基阳离子反应和自由基阴离子 Cope 反应和 Diels-Alder 反应。这项工作的目标是确定反应产物、它们形成的机制以及电离的催化作用。溶剂化离子将用于探测溶剂在确定反应产物中的作用。该提案概述了一个广泛的实验计划，以利用先进的流动余辉仪器和普渡大学目前正在建造的负离子光电子能谱仪的专业功能来表征各种离子自由基和相关新物种的结构和反应性。 虽然基于理论的计算将发挥作用，但主要重点显然是通过实验定义反应性的结构和模式。 该提议基于一位关心机械的物理有机化学家的好奇心，他完全具备经验丰富的气相离子化学家的更专业的技术储备。 应该获得许多新的信息和重要的概念进步。普渡大学化学系的 Paul Wenthold 教授在有机动力学项目的支持下，也将继续培训学生，他们将成为这项工作的研究和出版物中不可或缺的一部分。研究结果将为新型结构和化学转化提供新的理解，同时展示新兴技术/仪器能力的新应用。