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Inserting CO2 into Terminal Alkynes via Bis-(NHC)-Metal Complexes

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Abstract

The direct interaction between CO2 and terminal alkynes in the presence of bis-(NHC)-metal catalysts at ambient conditions was studied. Two Cu and Ag-based bis-N-heterocyclic carbene Transition Metal catalysts were synthesized. The (NHC)2-Ag complex showed a better catalytic performance towards the carboxylation of terminal alkynes in comparison with the copper analogue even for the conversion of acetylene gas. The optimized conditions for the carboxylation are: the use of Cs2CO3 as additive, one atmosphere CO2 and room temperature using 1% mol catalyst. Mechanistic insight into the reaction mechanism is obtained by means of state-of-the-art first principles calculations.

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Acknowledgements

F.V. acknowledges the Chinese Central Government for an “Expert of the State” position in the program of Thousand talents. H. D. V. acknowledges funding from the research funds of the Mexican Petroleum institute for a postdoctoral fellowship No. 90903. M.V. acknowledges funding from the Scientific Research-Foundation Flanders (FWO) for a postdoctoral fellowship. The computational resources and services used in this work were provided by VSC (Flemish Supercomputer Center), funded by the Hercules foundation and the Flemish Government—Department EWI. The authors would like to express their deep appreciation for financial support from the Natural Science Foundation of China (No. 21172027), the Fundamental Research Funds for the Central Universities (WUT: 2014-IV-099) and Independent Innovation Foundation of Wuhan University of Technology (No. 444-20510039).

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Authors and Affiliations

  1. Global Campus Songdo, Ghent University, 119 Songdomunhwa-Ro, Yeonsu-Gu, Incheon, South Korea

    Heriberto Díaz Velázquez & Francis Verpoort

  2. Dirección de investigación en Transformación de Hidrocarburos, Gerencia de Refinación de Hidrocarburos, Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas 152, 07730, México City, México

    Heriberto Díaz Velázquez

  3. School of materials, Material science and Engineering, State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Center for Chemical and Material Engineering, Wuhan University of Technology, Wuhan, 430070, People’s Republic of China

    Zhao-Xuan Wu

  4. Center for Molecular Modeling, Ghent University, Technologiepark 903, 9052, Zwijnaarde, Belgium

    Matthias Vandichel

  5. Laboratory of Organometallics, Catalysis and Ordered Materials, State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Center for Chemical and Material Engineering, Wuhan University of Technology, Wuhan, 430070, People’s Republic of China

    Francis Verpoort

  6. School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan, 430070, People’s Republic of China

    Francis Verpoort

  7. National Research Tomsk Polytechnic University, Lenin Avenue 30, 634050, Tomsk, Russian Federation

    Francis Verpoort

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  1. Heriberto Díaz Velázquez
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  2. Zhao-Xuan Wu
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  3. Matthias Vandichel
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  4. Francis Verpoort
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Correspondence to Heriberto Díaz Velázquez or Francis Verpoort.

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Díaz Velázquez, H., Wu, ZX., Vandichel, M. et al. Inserting CO2 into Terminal Alkynes via Bis-(NHC)-Metal Complexes. Catal Lett 147, 463–471 (2017). https://doi.org/10.1007/s10562-016-1920-5

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