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Published January 3, 2000 | public
Journal Article

Femtosecond Dynamics of Norrish Type-II Reactions: Nonconcerted Hydrogen-Transfer and Diradical Intermediacy


Norrish type-II and McLafferty rearrangements, which both involve an intramolecular transfer of a γ H atom, can be differentiated on the femtosecond time scale. The McLafferty rearrangement results in ion fragmentation of the parent ketone, whereas the Norrish type-II reaction leads to a diradical species, which then either cyclizes or fragments (see scheme). For Norrish type-II reactions, the reaction time for the transfer of the hydrogen atom is within 70 – 90 fs, and the lifetime of the diradical intermediate is in the range of 400 – 700 ps at the total energy studied.

Additional Information

© 2000 Wiley-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany. Received: September 23, 1999. Version of Record online: 12 Jan 2000. This work was supported by the US Airforce Office of Scientific Research and Office of Naval Research. S.D.F., a postdoctoral fellow of the Fund for Scientific Research-Flanders, acknowledges a Fulbright scholarship and financial support by the Katholieke Universiteit Leuven and by Caltech.

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