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Homoatomic Sulfur Cations 147 Fig. 7 Molecular orbitals of p symmetry in S42+ 7.1 Bonding in S42+ with 6p electrons The square planar S42+ dication (as well as its heavier homologues E42+ with E=Se and Te) was shown to be an inorganic 6p Hückel aromat; the S42+ mo- lecular orbitals of p symmetry are shown in Fig. 7. Overall the four atomic 3pz orbitals combine to one p bonding, two non- bonding and one anti bonding empty p* MO and in total one p bond is delo- calized over all four atoms giving a bond order of 1.25 which is in agreement with the by 5 pm shortened S-S distance in S42+ salts [5, 11] as well as with recent calculations [21]. 7.2 Bonding in S62+ with 10p Electrons The recently suggested D3d symmetric S62+ cation is also p bonded. Albeit not being completely planar, the 10p electrons reside in orbitals of local p symmetry and S62+ may be viewed as being a Hückel aromat with 10p elec- trons, although a strict differentiation between s- and p-MOs is impossible [3]. Removal of two electrons from the occupied 3p2 lone pair orbitals of the neutral S6 molecule with formally 12p electrons leads to one p bond delocal- ized over all six sulfur atoms. In agreement with this the S62+ dication ex- hibits an increased S-S-S bond angle a of 113.7 and a smaller S-S-S-S tor- sion angle t of 47.6 compared to S6 and S6+ (cf. S6: a=103.0, t=73.1; S6+: a=108.5, t=62.4; calculated values throughout for consistency; see Fig. 8a). The (calculated) S-S distance in S62+ is shortened from 2.050 in the clearly all s-bonded S8 molecule to 2.028 in 10p S62+. The electronic transition re- sponsible for the blue color of S62+ is of p*-p* nature and the S62+ molecular orbitals of p and p* symmetry are shown in Fig. 8b [28].PDF Image | Topics in Current Chemistry
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