TY  - JOUR
AU  - Ruan, Zilin
AU  - Fan, Qitang
AU  - Reichmann, Alexander
AU  - Kang, Faming
AU  - Naumann, Tim
AU  - Werner, Simon
AU  - Kleykamp, Olaf
AU  - Martinez-Castro, Jose
AU  - Lüpke, Felix
AU  - Haags, Anja
AU  - Bocquet, François C.
AU  - Kumpf, Christian
AU  - Soubatch, Serguei
AU  - Sundermeyer, Jörg
AU  - Puschnig, Peter
AU  - Tautz, F. Stefan
AU  - Gottfried, J. Michael
AU  - Wenzel, Sabine
TI  - Highly Structure‐Selective On‐Surface Synthesis of Isokekulene Versus Kekulene
JO  - Angewandte Chemie / International edition
VL  - 64
IS  - 36
SN  - 1433-7851
CY  - Weinheim
PB  - Wiley-VCH
M1  - FZJ-2025-03408
SP  - e202509932
PY  - 2025
AB  - 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.
LB  - PUB:(DE-HGF)16
C6  - 40629813
UR  - <Go to ISI:>//WOS:001538912000001
DO  - DOI:10.1002/anie.202509932
UR  - https://juser.fz-juelich.de/record/1044874
ER  -