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Synthesis of Cyclo[18]carbon via Debromination of C₁₈Br₆.

ABSTRACT: Cyclo[18]carbon (C₁₈, a molecular carbon allotrope) can be synthesized by dehalogenation of a bromocyclocarbon precursor, C₁₈Br₆, in 64% yield, by atomic manipulation on a sodium chloride bilayer on Cu(111) at 5 K, and imaged by high-resolution atomic force microscopy. This method of generating C₁₈ gives a higher yield than that reported previously from the cyclocarbon oxide C₂₄O₆. The experimental images of C₁₈ were compared with simulated images for four theoretical model geometries, including possible bond-angle alternation: D_18h cumulene, D_9h polyyne, D_9h cumulene, and C_9h polyyne. Cumulenic structures, with (D_9h) and without (D_18h) bond-angle alternation, can be excluded. Polyynic structures, with (C_9h) and without (D_9h) bond-angle alternation, both show a good agreement with the experiment and are challenging to differentiate.

SUBMITTER: Scriven LM

PROVIDER: S-EPMC7393637 | biostudies-literature | 2020 Jul

REPOSITORIES: biostudies-literature

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Synthesis of Cyclo[18]carbon via Debromination of C18Br6.

Scriven Lorel M LM Kaiser Katharina K Schulz Fabian F Sterling Alistair J AJ Woltering Steffen L SL Gawel Przemyslaw P Christensen Kirsten E KE Anderson Harry L HL Gross Leo L

Journal of the American Chemical Society 20200715 30

Cyclo[18]carbon (C18, a molecular carbon allotrope) can be synthesized by dehalogenation of a bromocyclocarbon precursor, C18Br6, in 64% yield, by atomic manipulation on a sodium chloride bilayer on Cu(111) at 5 K, and imaged by high-resolution atomic force microscopy. This method of generating C18 gives a higher yield than that reported previously from the cyclocarbon oxide C24O6. The experimental images of C18 were co ...[more]

PMID: 32646214

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Cyclo[18]carbon Formation from C18Br6 and C18(CO)6 Precursors.

Project description:Although cyclo[18]carbon has been isolated experimentally from two precursors, C18Br6 and C18(CO)6, no reaction mechanisms have yet been explored. Herein, we provide insight into the mechanism behind debromination and decarbonylation. Both neutral precursors demonstrate high activation barriers of ∼2.3 eV, while the application of an electric field can lower the barriers by 0.1-0.2 eV. The barrier energy of the anion-radicals is found to be significantly lower for C18Br6 compared to C18(CO)6, confirming a considerably higher yield of cylco[18]carbon when the C18Br6 precursor is used. Elongation of the C-Br bond in the anion-radical confirms its predissociation condition. Natural bonding orbital analysis shows that the stability of C-Br and C-CO bonds in the anion-radicals is lower compared to their neutral species, indicating a possible higher yield. The applied analysis provides crucial details regarding the reaction yield of cyclo[18]carbon and can serve as a general scheme for tuning reaction conditions for other organic precursors.

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Heavy-Atom Tunneling in the Covalent/Dative Bond Complexation of Cyclo[18]carbon-Piperidine.

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