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Chemical bonding in the hexamethylbenzene–SO2+ dication

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Abstract

A thorough bonding analysis is performed on the dication [C6(CH3)6SO]2+. The results show that the molecule is best described in terms of covalent interactions between the cations C6(CH3) +6 and SO+, whereby the bonding consists of two dominating contributions. The strongest bonding comes from dative interaction from the HOMO of C6(CH3) +6 to the LUMO of SO+, which has overall σ symmetry. The second significant component is due to electron-sharing bonding between the singly occupied orbitals of the two fragments. The bonding situation may be sketched with the formula \([{\text{C}_{6}}\text{(CH)}_{6}\overrightarrow{-}{\text{SO}}]^{2+}\). The bare dication is thermodynamically unstable with regard to dissociation into two cations. It is kinetically stable due to the activation barrier, and it is further stabilized by counterions.

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Acknowledgements

The authors acknowledge financial support by the Deutsche Forschungsgemeinschaft.

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  1. Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35032, Marburg, Germany

    Lisa Pecher, Sudip Pan & Gernot Frenking

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  1. Lisa Pecher
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  2. Sudip Pan
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  3. Gernot Frenking
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Correspondence to Gernot Frenking.

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Published as part of the special collection of articles derived from the 11th Congress on Electronic Structure: Principles and Applications (ESPA-2018).

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Pecher, L., Pan, S. & Frenking, G. Chemical bonding in the hexamethylbenzene–SO2+ dication. Theor Chem Acc 138, 47 (2019). https://doi.org/10.1007/s00214-019-2434-1

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