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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

Vijay K. Kanuru

Georgios Kyriakou

Simon K. Beaumont

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). doi:10.1021/ja1011542. ISSN 0002-7863

Journal Article Type Article
Acceptance Date Feb 8, 2010
Online Publication Date May 21, 2010
Publication Date Jun 16, 2010
Deposit Date Nov 13, 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
Keywords Colloid and Surface Chemistry; Biochemistry; General Chemistry; Catalysis
Public URL https://hull-repository.worktribe.com/output/466673
Publisher URL https://pubs.acs.org/doi/abs/10.1021/ja1011542