Cyclopropenium Cations Break the Rules of Attraction to FormClosely Bound Dimers
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The crystal structures of tris(ethylmethylamino)-cyclopropenium chloride and tris(diethylamino)-cyclopropenium iodide reveal the presence of closely bound dicationic dimers formed from two closed-shell monomer units. The distances between the C3 centroids of the staggered monomers are at the short end of those normally found in π-stacked neutral arenes, let alone charged aromatic rings. Computational analysis reveals that short-range interactions are dominated by strong dispersion forces, enabling metastable dicationic dimers to form without covalent intermolecular bonding. Surrounding counterions then provide a background source of charge balance, imparting strong thermodynamic stability to the system. Additionally, these counterions form a weak but attractive electrostatic bridge between the monomer units, contributing to the surprisingly short observed intermolecular C3-C3 centroid distance.
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Fields of Research::34 - Chemical sciences::3407 - Theoretical and computational chemistry::340701 - Computational chemistry
Fields of Research::34 - Chemical sciences::3402 - Inorganic chemistry::340202 - Crystallography
Fields of Research::34 - Chemical sciences::3402 - Inorganic chemistry::340208 - Non-metal chemistry
Fields of Research::34 - Chemical sciences::3405 - Organic chemistry::340505 - Physical organic chemistry