Surface‐Guided Formation of an Organocobalt Complex |
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| Authors: | Peter B Weber Raphael Hellwig Tobias Paintner Dr Marie Lattelais Mateusz Paszkiewicz Pablo Casado Aguilar Peter S Deimel Dr Yuanyuan Guo Dr Yi‐Qi Zhang Dr Francesco Allegretti Dr Anthoula C Papageorgiou Dr Joachim Reichert Dr Svetlana Klyatskaya Prof Dr Mario Ruben Prof Dr Johannes V Barth Dr Marie‐Laure Bocquet Dr Florian Klappenberger |
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| Affiliation: | 1. Physik Department E20, Technische Universit?t München, Garching, Germany;2. Ecole Normale Supérieure, PSL Research University, Département de Chimie, CNRS UMR, Paris, France;3. Karlsruher Institut für Technologie, Karlsruhe, Germany;4. IPCMS-CNRS, Université de Strasbourg, Strasbourg, France |
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| 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. |
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| Keywords: | alkynes density functional calculations organocobalt complexes scanning tunneling microscopy surface chemistry |
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