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The Reaction of Alkynes with Model Gold Catalysts: Generation of Acetylides, Self-coupling and Surface Decomposition

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Abstract

Alkynes are one of the most important groups of building blocks in organic chemistry as they work as nucleophiles upon deprotonation of its acidic hydrogen. On the surface of a gold catalyst the reactivity of an alkyne towards dehydrogenation depends on the stability of the resulting acetylide species and on its Brønsted acidic behavior with respect to other species in the system. Herein, we study the reaction of alkynes on an oxygen-covered gold surface, hereafter described as O/Au, with and without species able to build acid–base pairs on the surface. As expected, alkynes undergo a facile dehydrogenation process, forming acetylide species and coupling products such as CH3–CC–CC–CH3 from propyne (CH3–CC–H). However, temperature-programmed reactions show that the catalytic intermediates are strongly attached to the surface, leading to parallel decomposition pathways that result in the carbon poisoning of the catalyst. The strong attachment suggests that the alkynes can displace species known to undergo facile dehydrogenation on gold, such as adsorbed alkoxy, as demonstrated by experiments using selected alcohols and alkynes. Moreover, alkynes can even displace alcohols of similar molecular weight (acetylene vs. methanol; phenylacetylene vs. phenol). The results indicate that a gold catalyst facilitates the formation of acetylide species and coupling products, even though their strong interaction with the surface may be counterproductive, as it results in their decomposition.

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Acknowledgements

We would like to thank the valuable support of Prof. Cynthia Friend during the stages of experimental design, data analysis and for very fruitful discussions. Ms. Karinna Visurraga (UTEC) is acknowledged for administrative support.

Funding

This work was funded by UTEC Faculty Grant No. 819051 to promote international exploratory collaborative research with Harvard University. EM acknowledges the Ito Foundation for International Education Exchange for financial support. IMASC (Harvard) is acknowledged for partial support.

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Authors and Affiliations

  1. Department of Chemical Engineering, Universidad de Ingenieria y Tecnologia – UTEC, Jr. Medrano Silva 165, Barranco, Lima, 15063, Peru

    Danae A. Chipoco Haro & Juan Carlos F. Rodriguez-Reyes

  2. John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA

    Eri Muramoto & Robert J. Madix

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  1. Danae A. Chipoco Haro
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  2. Eri Muramoto
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  4. Juan Carlos F. Rodriguez-Reyes
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Correspondence to Juan Carlos F. Rodriguez-Reyes.

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Chipoco Haro, D.A., Muramoto, E., Madix, R.J. et al. The Reaction of Alkynes with Model Gold Catalysts: Generation of Acetylides, Self-coupling and Surface Decomposition. Catal Lett 152, 3066–3075 (2022). https://doi.org/10.1007/s10562-021-03882-4

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