The Role of Kinetics versus Thermodynamics in Surface-Assisted Ullmann Coupling on Gold and Silver Surfaces

Journal of the American Chemical Society
Massimo FrittonMarkus Lackinger

Abstract

Surface-assisted Ullmann coupling is the workhorse of on-surface synthesis. Despite its obvious relevance, many fundamental and mechanistic aspects remain elusive. To shed light on individual reaction steps and their progression with temperature, temperature-programmed X-ray photoelectron spectroscopy (TP-XPS) experiments are performed for a prototypical model system. The activation of the coupling by initial dehalogenation is tracked by monitoring Br 3d core levels, whereas the C 1s signature is used to follow the emergence of metastable organometallic intermediates and their conversion to the final covalent products upon heating in real time. The employed 1,3,5-tris(4-bromophenyl)benzene precursor is comparatively studied on Ag(111) versus Au(111), whereby intermolecular bonds and network topologies are additionally characterized by scanning tunneling microscopy (STM). Besides the well-comprehended differences in activation temperatures for debromination, the thermal progression shows marked differences between the two surfaces. Debromination proceeds rapidly on Ag(111), but is relatively gradual on Au(111). While on Ag(111) debromination is well explained by first-order reaction kinetics, thermodynamics prevail on Au(111), u...Continue Reading

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Citations

Apr 6, 2020·Physical Chemistry Chemical Physics : PCCP·Hui LuXueming Yang
Apr 28, 2020·Angewandte Chemie·Samuel StolzRoland Widmer
Oct 10, 2019·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Manabu OhtomoShintaro Sato
Feb 11, 2021·Scientific Reports·Jinping HuFei Song
Mar 6, 2021·Physical Chemistry Chemical Physics : PCCP·Jakub Lisiecki, Paweł Szabelski
Jul 9, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Markus Lackinger
Jul 10, 2021·Chemical Communications : Chem Comm·Cristina Martín-FuentesDavid Écija
Feb 20, 2020·The Journal of Physical Chemistry Letters·Hui LuXueming Yang
Oct 10, 2021·Nature Communications·Xinnan PengJiong Lu
Oct 7, 2021·Advanced Materials·Samuel StolzRoland Widmer
Dec 11, 2021·Nanoscale Horizons : the Home for Rapid Reports of Exceptional Significance in Nanoscience and Nanotechnolgy·Lukas GrossmannMarkus Lackinger

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