Albrecht, FlorianRey Vieites, Dulce MaríaFatayer, ShadiSchulz, FabianPérez Meirás, María DoloresPeña Gil, DiegoGross, Leo2021-01-152021-01-152020F. Albrecht, D. Rey, S. Fatayer, F. Schulz, D. Pérez, D. Peña, L. Gross, Angew. Chem. Int. Ed. 2020, 59, 229891433-7851http://hdl.handle.net/10347/24208Glaser‐like coupling of terminal alkynes by thermal activation is extensively used in on‐surface chemistry. Here we demonstrate an intramolecular version of this reaction performed by atom manipulation. We used voltage pulses from the tip to trigger a Glaser‐like coupling between terminal alkyne carbons within a custom‐synthesized precursor molecule adsorbed on bilayer NaCl on Cu(111). Different conformations of the precursor molecule and the product were characterized by molecular structure elucidation with atomic force microscopy and orbital density mapping with scanning tunneling microscopy, accompanied by density functional theory calculations. We revealed partially dehydrogenated intermediates, providing insight into the reaction pathwayeng© 2020 The Authors. Published by Wiley-VCH GmbH This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly citedAtribución 4.0 Internacionalhttp://creativecommons.org/licenses/by/4.0/Atomic force microscopyAtom manipulationC−C couplingOn-surface synthesisScanning tunneling microscopyjournal article10.1002/anie.2020092001521-3773open access