Reactive Noble-Gas\nCompounds Explored by 3D Electron\nDiffraction: XeF<sub>2</sub>–MnF<sub>4</sub> Adducts and a\nFacile Sample Handling Procedure

Recent advances in 3D electron diffraction (3D ED) have\nsucceeded\nin matching the capabilities of single-crystal X-ray diffraction (SCXRD),\nwhile requiring only submicron crystals for successful structural\ninvestigations. One of the many diverse areas to benefit from the\n3D ED structural analysis is main-group chemistry, where compounds\nare often poorly crystalline or single-crystal growth is challenging.\nA facile method for loading and transferring highly air-sensitive\nand strongly oxidizing samples at low temperatures to a transmission\nelectron microscope (TEM) for 3D ED analysis was successfully developed\nand tested on xenon(II) compounds from the XeF<sub>2</sub>–MnF<sub>4</sub> system. The crystal structures determined on nanometer-sized\ncrystallites by dynamical refinement of the 3D ED data are in complete\nagreement with the results obtained by SCXRD on micrometer-sized crystals\nand by periodic density-functional theory (DFT) calculations, demonstrating\nthe applicability of this approach for structural studies of noble-gas\ncompounds and highly reactive species in general. The compounds 3XeF<sub>2</sub>·2MnF<sub>4</sub>, XeF<sub>2</sub>·MnF<sub>4</sub>, and XeF<sub>2</sub>·2MnF<sub>4</sub> are rare examples of\nstructurally fully characterized xenon difluoride–metal tetrafluoride\nadducts and thus advance our knowledge of the diverse structural chemistry\nof these systems, which also includes the hitherto poorly characterized\nfirst noble-gas compound, “XePtF<sub>6</sub>”.