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Hannover 2013 – wissenschaftliches Programm

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MO: Fachverband Molekülphysik

MO 12: Femtosecond Spectroscopy III

MO 12.3: Vortrag

Dienstag, 19. März 2013, 14:45–15:00, F 102

Ultrafast photofragment ion spectroscopy of the Wolff rearrangement in 5-diazo Meldrum’s acid in the gas phaseAndreas Steinbacher, •Sebastian Roeding, Tobias Brixner, and Patrick Nuernberger — Institut für Physikalische und Theoretische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg

We investigate the multisequential photochemistry of 5-diazo Meldrum’s acid (DMA), a photoactive compound used in lithography, by femtosecond photofragment ion spectroscopy in the gas phase. Former studies [1,2] in solution revealed an ultrafast intramolecular Wolff rearrangement to a ketene after UV excitation, followed by subsequent reactions with a solvent molecule. In this gas phase study, the absence of interactions and reactions with solvent molecules allows us to focus on the photochemistry of the ketene intermediate. Besides direct fragmentation of this intermediate to acetone and carbon monoxide, we further find experimental indications that a second Wolff rearrangement occurs, as was conjectured earlier for this molecule [3] from photofragment analysis.
P. Rudolf, J. Buback, J. Aulbach, P. Nuernberger, and T. Brixner, JACS 2010, 132, 15213-15222
G. Burdzinski, J. Réhault, J. Wang, and M. S. Platz, J. Phys. Chem. A 2008, 112, 10108-10112
S. L. Kammula, H. L. Tracer, P. B. Shevlin, and M. Jones, J. Org. Chem. 1977, 42, 2931

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