TY - JOUR
T1 - Room-Temperature C-C σ-Bond Activation of Biphenylene Derivatives on Cu(111)
AU - Calupitan, Jan Patrick
AU - Wang, Tao
AU - Pérez Paz, Alejandro
AU - Álvarez, Berta
AU - Berdonces-Layunta, Alejandro
AU - Angulo-Portugal, Paula
AU - Castrillo-Bodero, Rodrigo
AU - Schiller, Frederik
AU - Peña, Diego
AU - Corso, Martina
AU - Pérez, Dolores
AU - de Oteyza, Dimas G.
N1 - Funding Information:
The authors acknowledge financial support from MCIN/AEI/10.13039/501100011033 (Grants PID2019-107338RB-C62, PID2019-107338RB-C63, PID2019-109555GB-I00, and TED2021-132388B-C43), the Basque Government (IT1591-22 and PIBA19-0004), the Spanish Research Council (ILINKC20002), the European Union’s Horizon 2020 research and innovation program (Grant 863098 and Marie Skłodowska-Curie Actions Individual Fellowship 101022150), and the Xunta de Galicia (Centro Singular de Investigación de Galicia, 2019-2022, Grant ED431G2019/03). A.P.P. thanks the UAEU for an internal start-up grant (31S410).
Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.
PY - 2023/2/2
Y1 - 2023/2/2
N2 - Activating 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 nanostructures.
AB - Activating 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 nanostructures.
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U2 - 10.1021/acs.jpclett.2c03346
DO - 10.1021/acs.jpclett.2c03346
M3 - Article
C2 - 36688740
AN - SCOPUS:85147113948
SN - 1948-7185
VL - 14
SP - 947
EP - 953
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 4
ER -