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138 Ingo Krossing Fig. 1 The solid state structures of all currently known structurally characterized sulfur cations Sn2+ (n=4, 8 19). Distances within the figure are given in . They originate from the crystal structures of S4(AsF6)2(AsF3) [11] (averaged according to local D4h symme- try), S8(AsF6)2 [23] (averaged assuming local Cs symmetry) and S19(SbF6)2 [12]. For comparison: the S-S distance of neutral S8 corrected for librational motion is 2.060 [13] From the structural data collected in Fig. 1 we note the following: (i) most of the S-S bond distances between the dicoordinate sulfur atoms are slightly shorter than those in neutral S8 [d(S-S)=2.060 [13], corrected for libra- tional motion]; (ii) the S-S bond lengths around the truly tricoordinate sul- fur atoms in S192+ are the longest of all S-S bond lengths in Fig. 1; (iii) in both, S82+ and S192+, a small bond lengths alternation is evident; (iv) in S82+ three rather odd weakly bonded transannular contacts occur at d(S-S)=2.85 to 3.00 . 4 Sulfur Cations in Solution The successive oxidation of sulfur by S2O6F2, oleum or AsF5 was monitored with several experimental techniques such as Magnetic Circular Dichroism (MCD) [14], UV/Vis spectroscopy [6], ESR spectroscopy [7], and magnetic measurements [4]. The last two methods pointed out the existence of singly charged radical cations Sn·+(n4) in equilibrium with the diamagnetic solid state cations S82+ and S192+, while pure S42+ solutions are ESR-silent. Of the detected radical(mono-)cations only S5·+ was unambiguously characterized on experimental grounds [7]. The lower the polarity of the solvent used toPDF Image | Topics in Current Chemistry
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