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Disulfuryl dichloride ClSO 2 OSO 2 Cl was characterized by vibrational spectroscopy in the gaseous and liquid phase as well as in the Ar-matrix. By varying the temperature, certain bands could be assigned to several conformers. Gas-phase electron diffraction revealed a dominance of the anti-conformer at ambient temperature. The same conformation was found in the solid state. Via the in situ technique for crystallization, not less than four different modifications were identified. Among these different modifications, the structural parameters of the molecules remain relatively constant, but the aggregation pattern changes. Although the molecules aggregate by chlorine⋅⋅⋅oxygen contacts in each modification, the geometrical parameters of these interaction show significant differences and were evaluated and are in part inconsistent with the halogen bonding concept., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

After numerous attempts over the last seven decades to obtain a structure for the simple, highly symmetric molecule tetranitromethane (C(NO 2 ) 4 , TNM) that is consistent with results from diffraction experiments and spectroscopic analysis, the structure has now been determined in the gas phase and the solid state. For the gas phase, a new approach based on a four-dimensional dynamic model for describing the correlated torsional dynamics of the four C-NO 2 units was necessary to describe the experimental gas-phase electron diffraction intensities. A model describing a highly disordered high-temperature crystalline phase was also established, and the structure of an ordered low-temperature phase was determined by X-ray diffraction. TNM is a prime example of molecular flexibility, bringing structural methods to the limits of their applicability., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Tris[tetrafluoro-4-(trifluoromethyl)phenyl]borane (BTolF) was prepared by treating boron tribromide with tetrameric F 3 CC 6 F 4 -Cu I . The F 3 CC 6 F 4 -Cu I was generated from F 3 CC 6 F 4 MgBr and copper(I) bromide. Lewis acidities of BTolF evaluated by the Gutmann-Beckett method and calculated fluoride-ion affinities are 9 and 10 %, respectively, higher than that of tris(pentafluorophenyl)borane (BCF) and even higher than that of SbF 5 . The molecular structures of BTolF and BCF were determined by gas-phase electron diffraction, that of BTolF also by single-crystal X-ray diffraction., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)