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Experimental and Theoretical Studies of Small Organic Dications, Molecules with Highly Remarkable Properties

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Structure/Reactivity and Thermochemistry of Ions

Part of the book series: NATO ASI Series ((ASIC,volume 193))

Abstract

Using the results of both, experiments as well as high level quantum chemical calculations the exciting properties of small doubly-charged cations in the gas phase are discussed. The comparison of experimental and theoretical data shows in almost all cases good to excellent agreement. All dications studied are thermochemically extremely unstable towards charge separation reactions. These unimolecular reactions are, however, associated with high activation barriers, thus kinetically stabilizing dications. As a consequence, the generation and detection of small dications are feasible in the gas phase. However, it is very unlikely that any of those dications will ever be generated in solution as viable species; instead, they will immediately oxidize or protonate the solvent shell, which is emphasized by the extremely high negative heats of proton or charge transfer reactions calculated for all small dications.

A reversal of the stability order of structural isomers, if compared with their neutral or monocationic counterparts, is frequently observed. Moreover, dications often favour equilibrium structures which differ significantly from those of the corresponding neutral isomers, like e.g. the preference for anti-van’t Hoff structures.

One of the origins of the stability reversal is the importance of donor-acceptor interactions, which is particularly pronounced for doubly-charged systems and which will be discussed in detail.

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  1. Institute of Organic Chemistry, Technical University Berlin, D-1000, Berlin 12, Germany

    Wolfram Koch & Helmut Schwarz

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  1. Center for Chemical Physics, National Bureau of Standards, Gaithersburg, Maryland, USA

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Koch, W., Schwarz, H. (1987). Experimental and Theoretical Studies of Small Organic Dications, Molecules with Highly Remarkable Properties. In: Ausloos, P., Lias, S.G. (eds) Structure/Reactivity and Thermochemistry of Ions. NATO ASI Series, vol 193. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-3787-1_21

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