Structural characterization and reactivity of a room-temperature-stable, 
antiaromatic cyclopentadienyl cation salt

Schulte, Yannick; Wölper, Christoph; Rupf, Susanne M.; Malischewski, Moritz; SantaLucia, Daniel J.; Neese, Frank; Haberhauer, Gebhard; Schulz, Stephan

doi:10.1038/s41557-023-01417-5

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Structural characterization and reactivity of a room-temperature-stable, antiaromatic cyclopentadienyl cation salt

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SantaLucia, Daniel J.
Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Neese, Frank
Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Schulte, Y., Wölper, C., Rupf, S. M., Malischewski, M., SantaLucia, D. J., Neese, F., et al. (2024). Structural characterization and reactivity of a room-temperature-stable, antiaromatic cyclopentadienyl cation salt. Nature Chemistry, 16(4), 651-657. doi:10.1038/s41557-023-01417-5.

Cite as: https://hdl.handle.net/21.11116/0000-000F-3882-F

Abstract

The singlet states of cyclopentadienyl (Cp) cations are considered as true prototypes of an antiaromatic system. Unfortunately, their high intrinsic reactivity inhibited their isolation in the solid state as a salt, and controlled reactions are also scarce. Here we present the synthesis and solid state structure of the room-temperature-stable Cp cation salt [Cp(C₆F₅)₅]⁺[Sb₃F₁₆]⁻. Although the aromatic triplet state of the [Cp(C₆F₅)₅]⁺ cation is energetically favoured in the gas phase according to quantum chemical calculations, coordination of the cation by either [Sb₃F₁₆]⁻ or C₆F₆ in the crystal lattice stabilizes the antiaromatic singlet state, which is present in the solid state. The calculated hydride and fluoride ion affinities of the [Cp(C₆F₅)₅]⁺ cation are higher than those of the perfluorinated tritylium cation [C(C₆F₅)₃]⁺. Reactions of [Cp(C₆F₅)₅]⁺[Sb₃F₁₆]⁻ with CO, which probably yields the corresponding carbonyl complex, and of radical Cp(C₆F₅)₅^∙ with selected model substrates (Cp₂Fe, (Ph₃C∙)₂ and Cp*Al) are also presented.