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Study of Concerted and Sequential Photochemical Wolff Rearrangement by Femtosecond UV−vis and IR Spectroscopy

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Quantum Electronics Laboratory, Faculty of Physics, Adam Mickiewicz University, 85 Umultowska, Poznan 61-614, Poland, and Department of Chemistry, The Ohio State University, Columbus, Ohio 43210
Cite this: J. Am. Chem. Soc. 2008, 130, 12, 3746–3747
Publication Date (Web):March 1, 2008
https://doi.org/10.1021/ja711346z
Copyright © 2008 American Chemical Society

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    Abstract

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    Photoinduced Wolff rearrangements were studied by femtosecond time-resolved UV−vis and IR transient absorption spectroscopy. For BpCN2COCH3 in acetonitrile the IR data indicate the presence of at least two mechanisms of ketene formation. The first process is fast proceeding in either 1BpCN2COCH3*, or in a hot carbene, or in both species, while the second is slow proceeding through the intermediacy of a relaxed carbene. The slow time constant of the ketene formation dynamics obtained by ultrafast IR (700 ps) spectroscopy agrees with the relaxed carbene decay of 800 ± 100 ps obtained by UV−vis absorption spectroscopy.

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     Adam Mickiewicz University.

     The Ohio State University.

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    Details of calculations (Tables S1 and S2) and transient spectra and kinetic traces (Figures S1−S3). This material is available free of charge via the Internet at http://pubs.acs.org.

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