3 years ago

The First Step of the Oxidation of Elemental Sulfur: Crystal Structure of the Homopolyatomic Sulfur Radical Cation [S8].+

The First Step of the Oxidation of Elemental Sulfur: Crystal Structure of the Homopolyatomic Sulfur Radical Cation [S8].+
Carsten Jenne, Janis Derendorf, Mathias Keßler
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 ([S4]2+, [S8]2+, and [S19]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 [S8].+ is presented. The radical cation [S8].+ represents the first step of the oxidation of the S8 molecule present in elemental sulfur. It has a structure similar to the known structure of [S8]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 [S8].+ is also in accord with previous ESR investigations. A radical step: Crystallographic evidence is presented for the new homopolyatomic sulfur radical cation [S8].+, which is the product of the first step of the oxidation of elemental sulfur. These results are supported by quantum-chemical calculations and confirm previously published ESR data.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201703083

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