Reactions of Atomic Carbon and Related High Energy Intermediates

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This grant in the Organic and Macromolecular Chemistry Program supports research by Prof. Philip Shevlin on the chemistry of atomic carbon and related high-energy organic reaction intermediates. Because atomic carbon possesses a large thermodynamic driving force for bond formation, it is a versatilereagent for preparation of selected, highly reactive species suchas carbenes. Thus, this work is useful both as a preparation method for some new high-energy chemical fragments, and for understanding the bonding and reactivity forces in others. In general, experiments are designed to prepare and elucidate thechemistry of monovalent carbon intermediates. Dr. Shevlin's recent work has shown that reaction of arc-generated carbon atomswith tetraflouromethane results in the formation of CF, which is observed to react with alkenes to generate flourocyclopropyl radicals. The products of the reaction of this interesting species with other substrates such as dienes and aromatic compounds will be identified in the coming work. Additional experiments are designed to investigate the chemistry of the other halomethynes and the parent species, CH. Other studies arebuilt around continuing investigations of novel carbenes generated as intermediates in C atom reactions. The reaction of carbon atoms with nitriles will be investigated with the goal of forming cyano- or isocyanocarbenes. The chemistry of aminomethylene will be investigated to determine if it undergoes reactions similar to the nucleophilic addition of hydroxymethylene to carbonyls, followed by hydrogent transfer. Lastly, experiments designed to investigate the reaction of atomic carbon with nonvolatile substrates in solution are planned.