Crystals of [MF3(XeF2)3]+ demonstrate new coordination chemistry in noble-gas fluorides, indicating potential expansions in this field.
Crystals of the double salts [Xe2F3][MF3(XeF2)3][AsF6]2 (M = Pd, Pt), prepared from anhydrous HF solutions, were characterized by low-temperature single-crystal X-ray diffraction and Raman spectroscopy. The crystal structures reveal that the compounds contain the hitherto unobserved [MF3(XeF2)3]+ adduct cations, which differ from all previously identified examples of XeF2 coordination to a metal(IV) center in their mononuclear and cationic nature, as well as in the coordination of multiple XeF2 ligands to a single metal(IV) center. Quantum-chemical calculations were performed to gain insight into the bonding and electronic structure of the [MF3(XeF2)3]+ adduct cations, with the optimized gas-phase geometries showing good agreement with the experimental solid-state structures. The characterized [MF3(XeF2)3]+ adduct cations markedly extend the chemistry of XeF2–MF4 systems and represent rare, crystallographically characterized examples of XeF2 coordination to PtIV and PdIV, a feature also believed to occur in the structure of the first discovered noble-gas compound, XePtF6. Moreover, the [MF3(XeF2)3]+ cations constitute the first examples of a new class of XeF2 coordination compounds, which are characterized by XeF2 ligation to a fluoridometal [MFx]n+ cation, thereby enabling further expansion of the coordination chemistry of noble-gas fluorides.
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Motaln et al. (2026) studied this question.
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