Absolute Kinetic Studies of Carbene Fragmentation and Related Reactions

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With this renewal award the Organic and Macromolecular Chemistry Program continues its support for the work of Dr. Robert A. Moss of the Department of Chemistry at Rutgers University New Brunswick campus in New Jersey. The research involves fundamental studies of carbenes and related reactive intermediates generated by laser flash photolysis, and followed by UV and IR absorption. Of particular interest is the study of the fragmentation reactions of alkoxyhalocarbenes (ROCX), where the rates and pathways are expected to depend on the natures of the R group and the halogen X. Quantum mechanical tunneling in intramolecular rearrangements will be studied using the cyclopropylmethyl carbenes C3H5CH2CCl and C3H5CD2CCl. High level computational studies carried out in collaboration with theoreticians will accompany the experimental work.This ongoing research involves fundamental studies of carbenes - short-lived and reactive intermediates with only two groups attached to carbon rather than the usual four - which can be generated in solution by very short laser flashes. The concentrations of the intermediates can then be followed by their absorption of ultraviolet or infrared light. This is classical physical organic chemistry, and is expected to provide excellent training for the students and colleagues involved, through the rigorous scientific approach used and the variety of strategies and techniques involved.