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Published November 24, 1994 | metadata_only
Journal Article

The Validity of the "Diradical" Hypothesis: Direct Femtosecond Studies of the Transition-State Structures


Direct studies of diradicals, the molecular species hypothesized to be archetypal of chemical bond transformations in many classes of reactions, have been made using femtosecond laser techniques with mass spectrometry in a molecular beam. These studies are aimed at "freezing" the diradicals in time and in the course of the reaction. The passage of these species through the transition-state region was observed and the effect of total energy and alkyl substitution on the rates of bond closure and cleavage was examined. The results establish the nature of these intermediates and define their existence during reactions.

Additional Information

© 1994 American Association for the Advancement of Science. 26 August 1994; accepted 23 September 1994. Supported by a grant from the Air Force Office of Scientific Research and by the National Science Foundation. We are grateful to P. B. Dervan, D. A. Dougherty, M. Okumura, J. D. Roberts, and W. von. E. Doering for the helpful discussions. We thank J. A. Berson and B. K. Carpenter for their helpful suggestions and penetrating questions, C. Doubleday Jr. for his interest in this work and for communicating unpublished results, K. Anderson for the preparation of 2,2,5,5-tetramethylcyclopentanone, and L. Banares for his help in the preliminary work (bulb studies) in this group. Contribution no. 8970 from the Arthur Amos Noyes Laboratory of Chemical Physics.

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August 20, 2023
August 20, 2023