title: Surface-Guided Formation of an Organocobalt Complex.
abstract: Organocobalt complexes represent a versatile tool in organic synthesis as they are important intermediates in Pauson-Khand, Friedel-Crafts, and Nicholas reactions. Herein, a single-molecule-level investigation addressing the formation of an organocobalt complex at a solid-vacuum interface is reported. Deposition of 4,4'-(ethyne-1,2-diyl)dibenzonitrile and Co atoms on the Ag(111) surface followed by annealing resulted in genuine complexes in which single Co atoms laterally coordinated to two carbonitrile groups undergo organometallic bonding with the internal alkyne moiety of adjacent molecules. Alternative complexation scenarios involving fragmentation of the precursor were ruled out by complementary X-ray photoelectron spectroscopy. According to density functional theory analysis, the complexation with the alkyne moiety follows the Dewar-Chatt-Duncanson model for a two-electron-donor ligand where an alkyne-to-Co donation occurs together with a strong metal-to-alkyne back-donation.
authors.affiliation: Physik Department E20, Technische Universität München, James-Franck-Str., 85748, Garching, Germany.
authors.forename: Peter B
authors.initials: PB
authors.lastname: Weber
authors.affiliation: Physik Department E20, Technische Universität München, James-Franck-Str., 85748, Garching, Germany.
authors.forename: Raphael
authors.initials: R
authors.lastname: Hellwig
authors.affiliation: Physik Department E20, Technische Universität München, James-Franck-Str., 85748, Garching, Germany.
authors.forename: Tobias
authors.initials: T
authors.lastname: Paintner
authors.affiliation: Ecole Normale Supérieure, PSL Research University, Département de Chimie, CNRS UMR, 8640 PASTEUR, 75005, Paris, France.
authors.forename: Marie
authors.initials: M
authors.lastname: Lattelais
authors.affiliation: Physik Department E20, Technische Universität München, James-Franck-Str., 85748, Garching, Germany.
authors.forename: Mateusz
authors.initials: M
authors.lastname: Paszkiewicz
authors.affiliation: Physik Department E20, Technische Universität München, James-Franck-Str., 85748, Garching, Germany.
authors.forename: Pablo
authors.initials: P
authors.lastname: Casado Aguilar
authors.affiliation: Physik Department E20, Technische Universität München, James-Franck-Str., 85748, Garching, Germany.
authors.forename: Peter S
authors.initials: PS
authors.lastname: Deimel
authors.affiliation: Physik Department E20, Technische Universität München, James-Franck-Str., 85748, Garching, Germany.
authors.forename: Yuanyuan
authors.initials: Y
authors.lastname: Guo
authors.affiliation: Physik Department E20, Technische Universität München, James-Franck-Str., 85748, Garching, Germany.
authors.forename: Yi-Qi
authors.initials: YQ
authors.lastname: Zhang
authors.affiliation: Physik Department E20, Technische Universität München, James-Franck-Str., 85748, Garching, Germany.
authors.forename: Francesco
authors.initials: F
authors.lastname: Allegretti
authors.affiliation: Physik Department E20, Technische Universität München, James-Franck-Str., 85748, Garching, Germany.
authors.forename: Anthoula C
authors.initials: AC
authors.lastname: Papageorgiou
authors.affiliation: Physik Department E20, Technische Universität München, James-Franck-Str., 85748, Garching, Germany.
authors.forename: Joachim
authors.initials: J
authors.lastname: Reichert
authors.affiliation: Karlsruher Institut für Technologie, Kaiserstraße 12, 76131, Karlsruhe, Germany.
authors.forename: Svetlana
authors.initials: S
authors.lastname: Klyatskaya
authors.affiliation: Karlsruher Institut für Technologie, Kaiserstraße 12, 76131, Karlsruhe, Germany.|IPCMS-CNRS, Université de Strasbourg, 23 rue de Loess, 67034, Strasbourg, France.
authors.forename: Mario
authors.initials: M
authors.lastname: Ruben
authors.affiliation: Physik Department E20, Technische Universität München, James-Franck-Str., 85748, Garching, Germany.
authors.forename: Johannes V
authors.initials: JV
authors.lastname: Barth
authors.affiliation: Ecole Normale Supérieure, PSL Research University, Département de Chimie, CNRS UMR, 8640 PASTEUR, 75005, Paris, France. marie-laure.bocquet@ens.fr.
authors.forename: Marie-Laure
authors.initials: ML
authors.lastname: Bocquet
authors.affiliation: Physik Department E20, Technische Universität München, James-Franck-Str., 85748, Garching, Germany. florian.klappenberger@tum.de.
authors.forename: Florian
authors.initials: F
authors.lastname: Klappenberger
keywords: alkynes; density functional calculations; organocobalt complexes; scanning tunneling microscopy; surface chemistry