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Homoatomic Sulfur Cations 149 Fig. 10a,b p and p*-p* bonding molecular orbitals in: a Se2I42+=(SeI2·+)2; b the struc- turally similar S82+ A further interaction that allows to delocalize the positive charge also onto the two apical sulfur atoms was found to be the 3p2!3s* hyperconjugation as shown in Fig. 11. With this interaction, initially suggested by Steudel et al. [30] to explain the bond length alternation in neutral S7, electron density from the occupied apical 3p2 lone pair orbitals is transferred into the empty 3s* orbitals of the vicinal S-S bonds. The overall process can be summarized as shown in Fig. 12. Starting from the classically expected structure with a short transannular bond and localized charges residing on the tricoordinate atoms the positive charges are delocalized over the central six sulfur atoms by a p*–p* interac- tion which is further responsible for the three weak transannular bonds. Ad- ditionally the positive charge is delocalized onto all atoms—as found in the experiment—by a further 3p2!3s* interaction. The combination of both in- Fig. 11 Further charge delocalization in S82+ by a 3p2!3s* interactionPDF Image | Topics in Current Chemistry
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