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Carbocatalytic Acetylene Cyclotrimerization: A Key Role of Unpaired Electron Delocalization

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    Carbocatalytic Acetylene Cyclotrimerization: A Key Role of Unpaired Electron Delocalization
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2020, 142, 8, 3784–3796
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    https://doi.org/10.1021/jacs.9b10887
    Published February 14, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    Development of sustainable catalysts for synthetic transformations is one of the most challenging and demanding goals. The high prices of precious metals and the unavoidable leaching of toxic metal species leading to environmental contamination make the transition metal-free catalytic systems especially important. Here we demonstrate that carbene active centers localized on carbon atoms at the zigzag edge of graphene represent an alternative platform for efficient catalytic carbon–carbon bond formation in the synthesis of benzene. The studied acetylene trimerization reaction is an efficient atom-economic route to build an aromatic ring—a step ubiquitously important in organic synthesis and industrial applications. Computational modeling of the reaction mechanism reveals a principal role of the reversible spin density oscillations that govern the overall catalytic cycle, facilitate the product formation, and regenerate the catalytically active centers. Dynamic π-electron interactions in 2D carbon systems open new opportunities in the field of carbocatalysis, unachievable by means of transition metal-catalyzed transformations. The theoretical findings are confirmed experimentally by generating key moieties of the carbon catalyst and performing the acetylene conversion to benzene.

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    Cite this: J. Am. Chem. Soc. 2020, 142, 8, 3784–3796
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.9b10887
    Published February 14, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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