Cyclopropenium Cations Break the Rules of Attraction to FormClosely Bound Dimers

Type of content
Journal Article
Thesis discipline
Degree name
Publisher
AMER CHEMICAL SOC
Journal Title
Journal ISSN
Volume Title
Language
English
Date
2015
Authors
Jayasinghe CD
Polson MIJ
Wallace, Andrew James
Curnow, Owen
Crittenden, Deborah
Abstract

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.

Description
Citation
Wallace 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.
Keywords
Science & Technology, Physical Sciences, Chemistry, Multidisciplinary, Chemistry, ION-PAIR STRAIN, ELECTRONIC-STRUCTURE, MOLECULAR-MECHANICS, DRIVING-FORCE, IODIDE-IONS, LONG BOND, LIQUIDS, MULTICENTER, SEGREGATION, BENZENE
Ngā upoko tukutuku/Māori subject headings
ANZSRC fields of research
03 Chemical Sciences
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
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