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

De Feyter, Steven and Diau, Eric W.-G. and Zewail, Ahmed H. (2000) Femtosecond Dynamics of Norrish Type-II Reactions: Nonconcerted Hydrogen-Transfer and Diradical Intermediacy. Angewandte Chemie International Edition, 39 (1). pp. 260-263. ISSN 1433-7851. https://resolver.caltech.edu/CaltechAUTHORS:20160819-142156777

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Abstract

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.


Item Type:Article
Related URLs:
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http://dx.doi.org/10.1002/(SICI)1521-3773(20000103)39:1<260::AID-ANIE260>3.0.CO;2-RDOIArticle
http://onlinelibrary.wiley.com/doi/10.1002/(SICI)1521-3773(20000103)39:1%3C260::AID-ANIE260%3E3.0.CO;2-R/abstractPublisherArticle
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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Funding AgencyGrant Number
Air Force Office of Scientific Research (AFOSR)UNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Fonds Wetenschappelijk Onderzoek - Vlaanderen (FWO)UNSPECIFIED
Fulbright CommissionUNSPECIFIED
Katholieke Universiteit LeuvenUNSPECIFIED
CaltechUNSPECIFIED
Subject Keywords:density functional calculations; diradicals; femtochemistry; hydrogen transfer; Norrish reactions
Issue or Number:1
Record Number:CaltechAUTHORS:20160819-142156777
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160819-142156777
Official Citation:De Feyter, S., Diau, E. W.-G. and Zewail, A. H. (2000), Femtosecond Dynamics of Norrish Type-II Reactions: Nonconcerted Hydrogen-Transfer and Diradical Intermediacy. Angew. Chem. Int. Ed., 39: 260–263. doi: 10.1002/(SICI)1521-3773(20000103)39:1<260::AID-ANIE260>3.0.CO;2-R
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:69799
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:22 Aug 2016 22:42
Last Modified:03 Oct 2019 10:25

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