%0 Journal Article
%A Ruan, Zilin
%A Fan, Qitang
%A Reichmann, Alexander
%A Kang, Faming
%A Naumann, Tim
%A Werner, Simon
%A Kleykamp, Olaf
%A Martinez-Castro, Jose
%A Lüpke, Felix
%A Haags, Anja
%A Bocquet, François C.
%A Kumpf, Christian
%A Soubatch, Serguei
%A Sundermeyer, Jörg
%A Puschnig, Peter
%A Tautz, F. Stefan
%A Gottfried, J. Michael
%A Wenzel, Sabine
%T Highly Structure‐Selective On‐Surface Synthesis of Isokekulene Versus Kekulene
%J Angewandte Chemie / International edition
%V 64
%N 36
%@ 1433-7851
%C Weinheim
%I Wiley-VCH
%M FZJ-2025-03408
%P e202509932
%D 2025
%X The role of different facets of metal nanoparticles in steering reaction pathways is crucial for the design ofheterogeneous catalysts with superior selectivity. As a prominent class of reactions, transition-metal-catalyzed carbon-hydrogen (C─H) bond activation is widely used for the synthesis of base chemicals, modern organic materials, andpharmaceuticals. Here, we report orthogonal selectivity in intramolecular cyclodehydrogenation of a nonplanar cyclicprecursor steered by different facets of a copper single crystal. On the Cu(110) surface, the previously unknown cycloareneisokekulene forms with a high selectivity of 92%, whereas reaction on the Cu(111) surface exclusively yields kekulene(>99%). Combining scanning tunneling microscopy with CO-functionalized tips and density functional theory, we identifytwo adsorption geometries of the precursor, which react to the respective products. Isokekulene adopts two nonplanaradsorption configurations and exhibits strong molecule-substrate interactions, explaining its preferential formation onCu(110). This combined in-solution and on-surface synthesis approach represents an alternative route for the highlyselective synthesis of molecules that are challenging to synthesize and process via conventional methods.
%F PUB:(DE-HGF)16
%9 Journal Article
%$ 40629813
%U <Go to ISI:>//WOS:001538912000001
%R 10.1002/anie.202509932
%U https://juser.fz-juelich.de/record/1044874