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Top Curr Chem (2003) 230:135–152 DOI 10.1007/b12112 Homoatomic Sulfur Cations Ingo Krossing Institut für Anorganische Chemie der Universität, 76128 Karlsruhe, Germany E-mail: krossing@chemie.uni-karlsruhe.de Abstract This chapter gives an account on the recent achievements in an understanding of the synthesis, solution behavior, structure and bonding of the homopolyatomic sulfur cat- ions. A focus is put on the developments aimed to understand experimental observations, i.e., quantum chemical calculations of these electronically delicate species. The synthesis of the highly electrophilic sulfur cations requires the use of very weakly basic conditions throughout, that is weakly coordinating counterions such as AsF6, SbF6, Sb2F11 as well as weakly basic solvents such as SO2, HF, HSO3F. Structure and bonding of the currently struc- turally characterized S42+, S82+, and S192+ cations are governed by positive charge delocaliza- tion brought about by 3pp-3pp, p*-p* and 3p2!3s* bonding interactions. The solution be- havior of S82+ salts, which give rise to several sulfur radical cations such as S5·+, was ana- lyzed in detail based on (calculated) thermodynamic as well as spectroscopic considerations and hitherto unknown D3d symmetric S62+ and D4h symmetric S4·+ are likely players in SO2 solutions of S8(AsF6)2. Keywords Sulfur · Cation · Ab initio · Bonding · DFT 1 Introduction................................... 136 1.1 HistoricalDevelopment............................ 136 2 Synthesis of Sulfur Cations in Condensed Phases . . . . . . . . . . . 137 3 SolidStateStructuresofSulfurCations . . . . . . . . . . . . . . . . . 137 4 SulfurCationsinSolution.......................... 138 5 GaseousSulfurCations............................ 139 5.1 SulfurMonocationsSn·+............................ 139 5.2 SulfurDicationsSn2+.............................. 140 5.2.1 TripletS32+ .................................... 140 5.2.2S42+Isomers................................... 141 5.2.3 Exo-EndoS82+.................................. 141 5.2.4 OtherSnm+Cations............................... 142 6 ThermodynamicsoftheSulfurCations................. 143 6.1 BasicThermochemicalData......................... 143 6.2 ThePreferenceofS42+ Over2S2•+ intheSolidState. . . . . . . . . . 143 6.3 Dissociation of Sn2+ (n=4, 6, 8, 10) in the Gas Phase andinSolution ................................. 144 Springer-Verlag Berlin Heidelberg 2003PDF Image | Topics in Current Chemistry
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