Insights in the Reaction Mechanistics: Isotopic Exchange During the Metalation of Deuterated Tetraphenyl-21,23D-porphyrin on Cu(111)

Röckert M, Franke M, Tariq Q, Lungerich D, Jux N, Stark MW, Kaftan A, Ditze S, Marbach H, Laurin M, Libuda J, Steinrück HP, Lytken O (2014)


Publication Type: Journal article

Publication year: 2014

Journal

Publisher: American Chemical Society

Book Volume: 118

Pages Range: 26729--26736

Volume: 118

DOI: 10.1021/jp507303h

Abstract

Using temperature-programmed desorption (TPD), the self-metalation and dehydrogenation of deuterated 5,10,15,20-tetraphenyl-21,23D-porphyrin on Cu(111) has been studied, resulting in new insight into the metalation of porphyrins on surfaces. The metalation is found to proceed through the transfer of the central aminic hydrogen atoms to the Cu(111) surface and not, as suggested by gas phase calculations, through the combination of the hydrogen atoms to molecular hydrogen above the partially inserted metal center. This finding suggests that the metalation reaction could be significantly influenced by the stability of hydrogen on the substrate surface. The metalation reaction and the subsequent hydrogenation and dehydrogenation of theperiphery of the porphyrin molecule leading to hydrogen-deuterium exchange are modeled with a simple microkinetic reaction model. The model is able to d escribe the main features of the TPD spectra.

Authors with CRIS profile

Additional Organisation(s)

How to cite

APA:

Röckert, M., Franke, M., Tariq, Q., Lungerich, D., Jux, N., Stark, M.W.,... Lytken, O. (2014). Insights in the Reaction Mechanistics: Isotopic Exchange During the Metalation of Deuterated Tetraphenyl-21,23D-porphyrin on Cu(111). Journal of Physical Chemistry C, 118, 26729--26736. https://doi.org/10.1021/jp507303h

MLA:

Röckert, Michael, et al. "Insights in the Reaction Mechanistics: Isotopic Exchange During the Metalation of Deuterated Tetraphenyl-21,23D-porphyrin on Cu(111)." Journal of Physical Chemistry C 118 (2014): 26729--26736.

BibTeX: Download