Catalytically Triggered Energy Release from Strained Organic Molecules: The Surface Chemistry of Quadricyclane and Norbornadiene on Pt(111)

Journal article
(Original article)


Publication Details

Author(s): Bauer U, Mohr S, Döpper T, Bachmann P, Späth F, Düll F, Schwarz M, Brummel O, Fromm L, Pinkert U, Görling A, Hirsch A, Bachmann J, Steinrück HP, Libuda J, Papp C
Journal: Chemistry - A European Journal
Publisher: Wiley-VCH Verlag
Publication year: 2017
Volume: 23
Journal issue: 7
Pages range: 1613-1622
ISSN: 0947-6539


Abstract


We have investigated the surface chemistry of the polycyclic valence-isomer pair norbornadiene (NBD) and quadricyclane (QC) on Pt(111). The NBD/QC system is considered to be a prototype for energy storage in strained organic compounds. By using a multimethod approach, including UV photoelectron, high-resolution X-ray photoelectron, and IR reflection-absorption spectroscopic analysis and DFT calculations, we could unambiguously identify and differentiate between the two molecules in the multilayer phase, which implies that the energy-loaded QC molecule is stable in this state. Upon adsorption in the (sub)monolayer regime, the different spectroscopies yielded identical spectra for NBD and QC at 125 and 160K, when multilayer desorption takes place. This behavior is explained by a rapid cycloreversion of QC to NBD upon contact with the Pt surface. The NBD adsorbs in a η:η geometry with an agostic Pt-H interaction of the bridgehead CH subunit and the surface. Strong spectral changes are observed between 190 and 220K because the hydrogen atom that forms the agostic bond is broke. This reaction yields a norbornadienyl intermediate species that is stable up to approximately 380K. At higher temperatures, the molecule dehydrogenates and decomposes into smaller carbonaceous fragments.



FAU Authors / FAU Editors

Bachmann, Julien Prof.
Lehrstuhl für Chemistry of thin film materials
Bachmann, Philipp
Lehrstuhl für Physikalische Chemie II
Bauer, Udo
Lehrstuhl für Physikalische Chemie II
Brummel, Olaf
Lehrstuhl für Physikalische Chemie II
Döpper, Tibor
Lehrstuhl für Theoretische Chemie
Düll, Fabian
Lehrstuhl für Physikalische Chemie II
Fromm, Lukas
Lehrstuhl für Theoretische Chemie
Görling, Andreas Prof. Dr.
Lehrstuhl für Theoretische Chemie
Hirsch, Andreas Prof. Dr.
Lehrstuhl für Organische Chemie II
Libuda, Jörg Prof. Dr.
Professur für Physikalische Chemie
Mohr, Susanne
Lehrstuhl für Physikalische Chemie II
Papp, Christian PD Dr.
Lehrstuhl für Physikalische Chemie II
Pinkert, Ute
Lehrstuhl für Organische Chemie II
Schwarz, Matthias
Lehrstuhl für Physikalische Chemie II
Späth, Florian
Lehrstuhl für Physikalische Chemie II
Steinrück, Hans-Peter Prof. Dr.
Lehrstuhl für Physikalische Chemie II


Additional Organisation
Interdisziplinäres Zentrum Erlangen Catalysis Resource Center (ECRC)
Exzellenz-Cluster Engineering of Advanced Materials


How to cite

APA:
Bauer, U., Mohr, S., Döpper, T., Bachmann, P., Späth, F., Düll, F.,... Papp, C. (2017). Catalytically Triggered Energy Release from Strained Organic Molecules: The Surface Chemistry of Quadricyclane and Norbornadiene on Pt(111). Chemistry - A European Journal, 23(7), 1613-1622. https://dx.doi.org/10.1002/chem.201604443

MLA:
Bauer, Udo, et al. "Catalytically Triggered Energy Release from Strained Organic Molecules: The Surface Chemistry of Quadricyclane and Norbornadiene on Pt(111)." Chemistry - A European Journal 23.7 (2017): 1613-1622.

BibTeX: 

Last updated on 2018-21-06 at 15:31