Calupitan, Jan PatrickWang, TaoPérez Paz, AlejandroÁlvarez Pérez, BertaBerdonces Layunta, AlejandroAngulo Portugal, PaulaCastrillo Bodero, RodrigoSchiller, FrederikPeña Gil, DiegoCorso, MartinaPérez Meirás, María DoloresOteyza, Dimas G. de2026-01-282026-01-282023-01-23J. P. Calupitan, T. Wang, A. Pérez Paz, B. Álvarez, A. Berdonces-Layunta, P. Angulo-Portugal, R. Castrillo-Bodero, F. Schiller, D. Peña, M. Corso, D. Pérez, D. G. de Oteyza J. Phys. Chem. Lett. 2023, 14, 947-953 (DOI: 10.1021/acs.jpclett.2c03346)1948-7185https://hdl.handle.net/10347/45526Activating the strong C–C σ-bond is a central problem in organic synthesis. Directly generating activated C centers by metalation of structures containing strained four-membered rings is one maneuver often employed in multistep syntheses. This usually requires high temperatures and/or precious transition metals. In this paper, we report an unprecedented C–C σ-bond activation at room temperature on Cu(111). By using bond-resolving scanning probe microscopy, we show the breaking of one of the C–C σ-bonds of a biphenylene derivative, followed by insertion of Cu from the substrate. Chemical characterization of the generated species was complemented by X-ray photoemission spectroscopy, and their reactivity was explained by density functional theory calculations. To gain further insight into this unique reactivity on other coinage metals, the reaction pathway on Ag(111) was also investigated and the results were compared with those on Cu(111). This study offers new synthetic routes that may be employed in the in situ generation of activated species for the on-surface synthesis of novel C-based nanostructureseng© 2023 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0.https://creativecommons.org/licenses/by/4.0/C—C σ-bond activationBiphenylenesMetalationOrganocopperScanning tunneling microscopyDensity functional theoryX-ray photoelectron spectroscopy2211 Física del estado sólido2211 Física del estado sólidojournal article10.1021/acs.jpclett.2c03346open access