A Direct Route to closo-SBnCln Thiaboranes: Chalcogen Bonding in SB5Cl5 vs. SB11Cl11 Crystals

Polyhedral boron chemistry exhibits various heteroatom substitution and a series of  heteroboranes thus being afforded Furthermore, the introduction of halogens instead of terminal hydrogens  enables the synthesis of small perhalogenated heteroboranes, stabilized through π back-donation. In this research, SB₅Cl₅ and SB₉Cl₉ clusters were prepared by co-pyrolysis of B₂Cl₄ with S₂Cl₂ at 280 °C in a vacuum. These substances were confirmed by high-resolution mass spectrometry and ¹¹B NMR spectroscopy, and two structures were verified by X-ray diffraction. Subsequently, their properties were compared with further chalcogenaboranes of such structural motifs. It is only sulfur that enables to detect other structural motifs than  those above. In particular, 13-vertex SB₁₂Cl₁₂ has been verified. The involvement of the computational department plays a crucial role in predicting the possibility of compound formation and subsequently evaluating their structure, behavior, and properties.

https://onlinelibrary.wiley.com/doi/10.1002/anie.202406751