Controlling Reactivity-Real-Space Imaging of a Surface Metal Carbene.

Autor: Mieres-Perez J; Universität Duisburg-Essen, Computational Biochemistry, Universitätsstr.2, D-45141 Essen, Germany., Lucht K; Ruhr-Universität Bochum, Lehrstuhl für Physikalische Chemie I, Universitätsstr.150, D-44801 Bochum, Germany., Trosien I; Ruhr-Universität Bochum, Lehrstuhl für Organische Chemie II, Universitätsstr.150, D-44801 Bochum, Germany., Sander W; Ruhr-Universität Bochum, Lehrstuhl für Organische Chemie II, Universitätsstr.150, D-44801 Bochum, Germany., Sanchez-Garcia E; Universität Duisburg-Essen, Computational Biochemistry, Universitätsstr.2, D-45141 Essen, Germany., Morgenstern K; Ruhr-Universität Bochum, Lehrstuhl für Physikalische Chemie I, Universitätsstr.150, D-44801 Bochum, Germany.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2021 Mar 31; Vol. 143 (12), pp. 4653-4660. Date of Electronic Publication: 2021 Feb 18.
DOI: 10.1021/jacs.0c12995
Abstrakt: Metal carbenes are key intermediates in a plethora of homogeneous and heterogeneous catalytic processes. However, despite their importance to heterogeneous catalysis, the influence of surface attachment on carbene reactivity has not yet been explored. Here, we reveal the interactions of fluorenylidene (FY), an archetypical aromatic carbene of extreme reactivity, with a Ag(111) surface. For the first time, the interaction of a highly reactive carbene with a metal surface could be studied by scanning tunneling microscopy (STM). FY chemisorbs on Ag(111) with an estimated desorption energy of 3 eV, forming a surface bound silver-carbene complex. The surface interaction leads to a switching of the electronic ground state of FY from triplet to singlet, and to controlled chemical reactivity. This atomistic understanding of the interplay between carbenes and metal surfaces opens the way for the development of novel classes of catalytic systems based on surface metal carbenes.
Databáze: MEDLINE