Cyclopropenium Cations Break the Rules of Attraction to FormClosely Bound Dimers (2015)
Type of ContentJournal Article
PublisherAMER CHEMICAL SOC
- Science: Journal Articles 
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.
CitationWallace AJ, Jayasinghe CD, Polson MIJ, Curnow OJ, Crittenden DL (2015). Cyclopropenium Cations Break the Rules of Attraction to Form Closely Bound Dimers. Journal of the American Chemical Society. 137(49). 15528-15532.
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KeywordsScience & Technology; Physical Sciences; Chemistry, Multidisciplinary; Chemistry; ION-PAIR STRAIN; ELECTRONIC-STRUCTURE; MOLECULAR-MECHANICS; DRIVING-FORCE; IODIDE-IONS; LONG BOND; LIQUIDS; MULTICENTER; SEGREGATION; BENZENE
ANZSRC Fields of Research34 - Chemical sciences::3407 - Theoretical and computational chemistry::340701 - Computational chemistry
34 - Chemical sciences::3402 - Inorganic chemistry::340202 - Crystallography
34 - Chemical sciences::3402 - Inorganic chemistry::340208 - Non-metal chemistry
34 - Chemical sciences::3405 - Organic chemistry::340505 - Physical organic chemistry
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