Reactive Intermediates from Carbene Fragmentation

Rutgers University New Brunswick, New Brunswick NJ

Investigators

Abstract

With the support of the Organic Dynamics Program in the Chemistry Division, Professors Robert A. Moss of Rutgers University will continue fundamental studies of organic reactive intermediates, particularly carbenes and carbocations using direct spectroscopic and fast kinetics methodologies. More specifically, the fragmentation of carbenes will be studied as a novel entry to numerous carbocations of special structural significance. Mechanism(s) of formation, solvent equilibration, and the kinetics of reaction will be examined and compared with results obtained from older and more traditional methods of carbocation generation. The role of ion pairs in heterolytic carbene fragmentation reactions will be closely examined as well as examples of homolytic fragmentation. Matrix isolation methods will be employed in some of these cases. The research results should enhance our ability to diagnose the interplay between polar concerted fragmentation transition states, tight or contact ion pairs, solvent equilibrated ion pairs, and radical pairs in carbene fragmentation reactions. It should also contribute to defining the reactivity and properties of many of the classic carbocations of physical organic chemistry as generated by a non-solvolytic procedure. The Organic and Macromolecular Chemistry Program supports Professors Robert A. Moss of Rutgers University who will attempt to answer fundamental questions on carbene fragmentation, and examining its mechanism(s) and application to the generation of carbocations, ion pair, or related intermediates in organic systems. Professor Moss will gather a team of collaborators who will assist in answering these questions using fast kinetics methodology, product analysis and computational methods. He will continue to have a broad impact on the physical organic chemistry community by distributing the results of his research through publications and writing scholarly review articles. Professor Moss along with two co-authors will edit Reactive Intermediate Chemistry, a book of 22 chapters devoted to a comprehensive study of reactive intermediates that is intended for graduate students and professional chemists.