Absolute Kinetic Studies of Intramolecular and Intermolecular Carbenic Reactions

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This grant from the Organic Dynamics Program supports the continuing work of Professor Robert A. Moss at Rutgers University. Carbenes and related reactive intermediates will be studied by direct spectroscopic methods, particularly by laser flash photolysis. Elements of the project are: (1) dissection of the photoinitiated carbenic reactions to reveal contamination by excited state precursors (carbene mimetic reactions); (2) examination of isotope effects on intramolecular rearrangements, and evidence for tunneling; (3) the study of electronic and steric effects in competitive 1,2-carbon migrations of unsymmetrically ring-substituted cyclopropylhalocarbenes; (4) the measurement of the electronic character of 1,2-acyl migrations in acyloxycarbenes and the possible generation of acyl anions by the basic cleavage of acyloxydiazirenes; and (5) determination of the kinetics of carbene-pyridine ylide formation. Carbenes, divalent carbon species, are important reactive intermediates in organic chemistry. Aspects of the reactions of carbenes will be studied such as the mode of hydrogen and carbon atom migrations and the origin of the products of photolysis of carbene precursors. This research could lead to new insights in our understanding of carbene chemistry.