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O: Fachverband Oberflächenphysik

O 83: Surface Chemistry and Growth

O 83.3: Vortrag

Donnerstag, 19. März 2015, 11:00–11:15, MA 144

Metalation of deuterated tetraphenylporphyrin on Cu(111): Insights into the reaction pathway — •Ole Lytken, Michael Röckert, Matthias Franke, Quratulain Tariq, Stefanie Ditze, Michael Stark, Andre Kaftan, Dominik Lungerich, Norbert Jux, Mathias Laurin, Jörg Libuda, Hubertus Marbach, and Hans-Peter Steinrück — Universität Erlangen-Nürnberg

Temperature-Programmed Desorption (TPD) of the metalation of deuterated 5,10,15,20-tetraphenyl-21,23D-porphyrin on Cu(111) reveals that the metalation reaction proceeds through the transfer of the central aminic deuterium atoms to the Cu(111) surface and not, as might be expected from gas phase calculations, through the combination of the hydrogen atoms to molecular hydrogen above the partial inserted metal center. Experimentally, desorption of mostly hydrogen and very little deuterium is observed as the deuterated porphyrin molecule metalates. Despite the absence of deuterium in the periphery of the molecule before metalation, desorption of deuterium is not observed until the periphery dehydrogenates at higher temperatures. This is caused by hydrogenation and dehydrogenation of the periphery of the molecule exchanging deuterium produced during metalation with hydrogen from the periphery. The reactions have been modeled with a simple micro kinetic model able to describe the main features of the TPD spectra.