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While reactions between ions and neutral molecules in the gas phase have been studied extensively, reactions between molecular ions of same polarity remain relatively unexplored. Herein we show that reactions between fragment ions generated in the gas phase and molecular ions of the same polarity are possible by soft-landing of both reagents on surfaces. The reactive [B 12 I 11 ] 1- anion was deposited on a surface layer built up by landing the generally unreactive [B 12 I 12 ] 2- . Ex-situ analysis of the generated material shows that [B 24 I 23 ] 3- was formed. A computational study shows that the product is metastable in the gas phase, but a charge-balanced environment of a grounded surface may stabilize the triply charged product, as suggested by model calculations. This opens new opportunities for the generation of highly charged clusters using unconventional building blocks from the gas phase., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The oxidation of elemental sulfur in superacidic solutions and melts is one of the oldest topics in inorganic main group chemistry. Thus far, only three homopolyatomic sulfur cations ([S 4 ] 2+ , [S 8 ] 2+ , and [S 19 ] 2+ ) have been characterized crystallographically although ESR investigations have given evidence for the presence of at least two additional homopolyatomic sulfur radical cations in solution. Herein, the crystal structure of the hitherto unknown homopolyatomic sulfur radical cation [S 8 ] .+ is presented. The radical cation [S 8 ] .+ represents the first step of the oxidation of the S 8 molecule present in elemental sulfur. It has a structure similar to the known structure of [S 8 ] 2+ , but the transannular sulfur⋅⋅⋅sulfur contact is significantly elongated. Quantum-chemical calculations help in understanding its structure and support its presence in solution as a stable compound. The existence of [S 8 ] .+ is also in accord with previous ESR investigations., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

It is common and chemically intuitive to assign cations electrophilic and anions nucleophilic reactivity, respectively. Herein, we demonstrate a striking violation of this concept: The anion [B 12 Cl 11 ] - spontaneously binds to the noble gases (Ngs) xenon and krypton at room temperature in a reaction that is typical of "superelectrophilic" dications. [B 12 Cl 11 Ng] - adducts, with Ng binding energies of 80 to 100 kJ mol -1 , contain B-Ng bonds with a substantial degree of covalent interaction. The electrophilic nature of the [B 12 Cl 11 ] - anion is confirmed spectroscopically by the observation of a blue shift of the CO stretching mode in the IR spectrum of [B 12 Cl 11 CO] - and theoretically by investigation of its electronic structure. The orientation of the electric field at the reactive site of [B 12 Cl 11 ] - results in an energy barrier for the approach of polar molecules and facilitates the formation of Ng adducts that are not detected with reactive cations such as [C 6 H 5 ] + . This introduces the new chemical concept of "dipole-discriminating electrophilic anions.", (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)