From thiocarbonyl dihalides to their carbocation derivatives - synthesis, structure and bonding.

Authors

Hennes Günther, Sven Ringelband, Franka Rischer, Frank Tambornino

Published in

Dalton transactions (Cambridge, England : 2003). Jul 14, 2026. Epub Jul 14, 2026.

Abstract

The dimer of thiocarbonyl dibromide was prepared via bromination of CSCl₂ followed by sunlight irradiation or by solvent-free bromination of C₂S₂Cl₄. Thermal induced cycloreversion at 155 °C affords light sensitive red liquid CSBr₂, as confirmed by ¹³C NMR spectroscopy (135.4 ppm). In situ single-crystal X-ray diffraction reveals disorder of Br/S atom positions, resulting in hexagonal spacegroup P6₃/m. Halide abstraction of C₂S₂Cl₄ and C₂S₂Br₄, yields glovebox-stable carbocations [C₂S₂X₃]⁺, accessible via salt elimination or Lewis acid base reaction. Comparison with the respective neutral dimers shows bond contraction and planarization, while computational analysis of [C₂S₂X₃]⁺ and C₂S₂X₄ (X = F-I) reveals halogen dependend σ bond contribution and atomic charges.

PMID:
42446900
Bibliographic data and abstract were imported from PubMed on 14 Jul 2026.

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