Studies of Ionic Pericyclic Reactions in the Gas Phase

在化学系有机动力学项目的支持下，普渡大学化学系的保罗·温托尔德教授将利用流动余辉/光电子能谱研究离子的周环反应。所研究的反应包括自由基阳离子和自由基阴离子Cope反应和Diels-Alder反应。这项工作的目标将是确定反应的产物，它们的形成机理，以及电离的催化作用。将使用溶剂化离子来探索溶剂在测定反应产物中的作用。该提案概述了一项广泛的实验计划，以表征各种离子自由基和相关新物种的结构和反应性，使用先进的流动余辉仪器和目前正在普渡大学建造的负离子光电子能谱仪的专门能力。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来定义反应性的结构和模式。这项提议是基于一位机械相关的物理有机化学家的好奇心，他完全配备了经验丰富的气相离子化学家的更专门的技术手段。应该获得许多新的信息和不平凡的概念进展。普渡大学化学系的保罗·温托尔德教授在有机动力学项目的支持下，也将继续培训学生，这些学生将成为这项工作所产生的研究和出版物的组成部分。研究结果将提供对新结构和化学转化的新理解，同时展示新兴技术/仪器能力的新应用。

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.