Hannover 2016 – wissenschaftliches Programm
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MO: Fachverband Molekülphysik
MO 7: Femtosecond Spectroscopy 2
MO 7.2: Vortrag
Dienstag, 1. März 2016, 11:30–11:45, f102
Pursuing Primary Processes of Diphenylcarbene in Binary Solvent Mixtures — •Johannes Knorr1, Pandian Sokkar2, Sebastian Schott3, Paolo Costa4, Wolfram Sander4, Elsa Sánchez-García2, and Patrick Nuernberger1 — 1Physikalische Chemie II, Ruhr-Universität Bochum, 44780 Bochum — 2Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr — 3Institut für Physikalische und Theoretische Chemie, Am Hubland, Universität Würzburg, 97074 Würzburg — 4Organische Chemie II, Ruhr-Universität Bochum, 44780 Bochum
The ultrafast reaction dynamics of carbenes in solution are governed by intersystem crossings, intermolecular proton uptake, or concerted reactions with the solvent. In this study, we combine quantum mechanics/molecular mechanics calculations and broadband femtosecond transient absorption spectroscopy applied to diphenylcarbene, and unravel the underlying dynamics and reaction mechanisms that take place in binary solvent mixtures at room temperature. The results show that a competition between the reaction pathways occurs that not only depends on the solvent molecule near-by but also on its interaction with other solvent molecules. In-depth analysis of the solvation dynamics and the amount of nascent intermediates corroborates the importance of a hydrogen-bonded complex with a protic solvent molecule, in striking analogy to complexes found at cryogenic temperatures [1].
P. Costa and W. Sander, Angew. Chem. 2014, 53, 5122-5125