Studies of Ionic Pericyclic Reactions in the Gas Phase

Purdue University, West Lafayette IN

Investigators

Abstract

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.