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148 Ingo Krossing Fig. 8 a Structural changes upon oxidation of S6 to S62+. b Top view of the S62+ molecular orbitals of local p and p* symmetry with the HOMO-LUMO transition of p*-p* symme- try being the reason for the intense blue color of S62+ in solution 7.3 Bonding in S82+ The overall structure of exo-endo S82+ was not unexpected since it is inter- mediate between the structure of crown (exo-exo) S8 and endo-endo S4N4 (isolectronic with S84+) as shown in Fig. 9: Fig. 9 Structural relationships between S8, S82+ and S84+ However, the long transannular bonds at 2.85 to 3.00 and the entirely delocalized charges are not accounted for by this model. Since the central six atoms of S82+ have a similar structural arrangement as the six atoms of Se2I42+=(SeI2·+)2 it was postulated that the bonding in S82+ should be related and due to a p*-p* interaction; see Fig. 10a. Later [23] it was verified that the weak cross ring bonds are due to a weakly bonding p*-p* interaction [29] of the partially occupied 3p orbitals of the six central sulfur atoms of the S82+ dication (HOMO in Fig. 10b). An interaction as shown in Fig. 10b leads to a delocalization of one p bond over the central six sulfur atoms and the two halves of the HOMO, which is best described as being of p* nature, provide a non-cancelled weak- ly bonding interaction between the three transannular pairs of sulfur atoms.PDF Image | Topics in Current Chemistry
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