Coordination of XeF2 to Fluoridometal Cations: The Adduct Cations [PtF3(XeF2)3]+ and [PdF3(XeF2)3]+

Single-crystal X-ray diffraction Single-crystal X-ray diffraction data were collected at a temperature of −173 °C on a Rigaku OD XtaLAB Synergy-S diffractometer equipped with a Dectris EIGER2 R CdTe 1M hybrid pixel array detector using microfocused Ag Kα radiation (λ = 0.56087 Å). CrysAlisPro software was employed for data processing, utilizing empirical and numerical absorption correction [1]. The crystal structure of [Xe2F3][PtF3(XeF2)3][AsF6]2(oP256) was solved using SUPERFLIP [2], whereas the crystal structures of [Xe2F3][PtF3(XeF2)3][AsF6]2(aP256) and [Xe2F3][PdF3(XeF2)3][AsF6]2 were solved using SHELXT [3]. All three structures were refined with SHELXL [4] within Olex2 software [5]. SCXRD-data folder: The supplied data comprise the raw diffraction images in .odeiger format, the associated data reduction and processing files, and the structure solution files. Raman Spectroscopy Low-temperature Raman spectra were measured at 100 K on a Bruker Senterra II confocal Raman microscope coupled with a Linkam LTS420 low-temperature stage, using a 785-nm emission line. The spectra were measured in the 50–1410 cm−1 range with a resolution of 1.5 cm−1. Prior to analysis, the samples were coarsely homogenized in an agate mortar within a glovebox and loaded into F2-passivated quartz capillaries (500 µm diameter), which were subsequently flame-sealed in a hydrogen–oxygen flame. The final spectra reported in the publication were obtained by averaging several baseline-substracted spectra from multiple distinct randomly-oriented crystallites. Baseline subtraction using 3 iterations of concave rubber band correction with 64 baseline points and spectral averaging were performed in Bruker Opus 8.7 software suite. Complete set of parameters for each measurement is given below: [Xe2F3][PtF3(XeF2)3][AsF6]2(oP256) (labelled as XePtAs_oP) – 50 µm aperture, 25 mW laser power, 20x objective, averaged from 7 spectra. [Xe2F3][PtF3(XeF2)3][AsF6]2(aP256) (labelled as XePtAs_aP) – 50 µm aperture, 50 mW laser power, 20x objective, averaged from 7 spectra. [Xe2F3][PdF3(XeF2)3][AsF6]2 (labelled as XePdAs) – 50 µm aperture, 50 mW laser power, 20x objective, averaged from 13 spectra. Raman-data folder: The subfolders labeled "processed" and "raw" contain, respectively, the final averaged Raman spectra and the individual spectra prior to baseline subtraction. All spectra are provided in the comma-delimited .dpt file format. Note: the broad features observed in the 1100–1300 cm−1 region in some of the spectra are measurement artefacts, most likely originating from the use of the quartz capillaries, and not a component of the Raman spectra of the compounds. ATR-IR Spectroscopy Infrared spectra were measured inside an N2 atmosphere glovebox on a Bruker Alpha II FT-IR spectrometer equipped with a Platinum Diamond-ATR sampling module. Prior to analysis, the compounds were finely ground in an agate mortar. Spectra were recorded in the range of 400–4000 cm−1 with a resolution of 4 cm−1 and 24 scans taken per measurement. ATR-IR-data folder: The submitted data consists of unprocessed ATR-IR spectra, given in the comma-delimited .dpt file format. DFT calculations Quantum chemical calculations were carried out using DFT as implemented in ORCA software (version 6.0.0) [6–8]. The electronic structures of [MF3(XeF2)3]+ cations were calculated starting from the crystallographic coordinates and resulted in stationary points with all frequencies real. The calculations were performed using the PBE0-D3/aug-cc-pVQZ method [9–12] with SK-MCDHF-RSC ECPs and aug-cc-pVQZ-PP basis sets for heavy atoms, namely Pd [13], Pt [14], and Xe [15]. Raman spectra were calculated using the numerical frequency calculations (!NumFreq) together with the polarizability calculation (%elprop Polar 1 end) [16]. DFT-data folder: The dataset includes optimized cartesian coordinates (.xyz), ORCA binary wavefunction file (.gbw), Hessian (force constant matrix) file from frequency calculation (.hess), and ORCA Output File containing calculated vibrational frequencies (.out) for the [MF3(XeF2)3]+ and [MF3]3+ cations, and the [MF6]2− anions (M = Pt, Pd).