Vijay K. Kanuru
Sonogashira Coupling on an Extended Gold Surface in Vacuo: Reaction of Phenylacetylene with Iodobenzene on Au(111)
Kanuru, Vijay K.; Kyriakou, Georgios; Beaumont, Simon K.; Papageorgiou, Anthoula C.; Watson, David J.; Lambert, Richard M.
Authors
Georgios Kyriakou
Dr Simon Beaumont simon.beaumont@durham.ac.uk
Associate Professor
Anthoula C. Papageorgiou
David J. Watson
Richard M. Lambert
Abstract
Temperature-programmed reaction measurements supported by scanning tunneling microscopy have shown that phenylacetylene and iodobenzene react on smooth Au(111) under vacuum conditions to yield biphenyl and diphenyldiacetylene, the result of homocoupling of the reactant molecules. They also produce diphenylacetylene, the result of Sonogashira cross-coupling, prototypical of a class of reactions that are of paramount importance in synthetic organic chemistry and whose mechanism remains controversial. Roughened Au(111) is completely inert toward all three reactions, indicating that the availability of crystallographically well-defined adsorption sites is crucially important. High-resolution X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy show that the reactants are initially present as intact, essentially flat-lying molecules and that the temperature threshold for Sonogashira coupling coincides with that for C−I bond scission in the iodobenzene reactant. The fractional-order kinetics and low temperature associated with desorption of the Sonogashira product suggest that the reaction occurs at the boundaries of islands of adsorbed reactants and that its appearance in the gas phase is rate-limited by the surface reaction. These findings demonstrate unambiguously and for the first time that this heterogeneous cross-coupling chemistry is an intrinsic property of extended, metallic pure gold surfaces: no other species, including solvent molecules, basic or charged (ionic) species are necessary to mediate the process.
Citation
Kanuru, V. K., Kyriakou, G., Beaumont, S. K., Papageorgiou, A. C., Watson, D. J., & Lambert, R. M. (2010). Sonogashira Coupling on an Extended Gold Surface in Vacuo: Reaction of Phenylacetylene with Iodobenzene on Au(111). Journal of the American Chemical Society, 132(23), 8081-8086. https://doi.org/10.1021/ja1011542
Journal Article Type | Article |
---|---|
Publication Date | May 21, 2010 |
Deposit Date | Nov 27, 2012 |
Publicly Available Date | Apr 15, 2014 |
Journal | Journal of the American Chemical Society |
Print ISSN | 0002-7863 |
Electronic ISSN | 1520-5126 |
Publisher | American Chemical Society |
Peer Reviewed | Peer Reviewed |
Volume | 132 |
Issue | 23 |
Pages | 8081-8086 |
DOI | https://doi.org/10.1021/ja1011542 |
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Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/ja1011542.
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