Reductive syntheses of transition metal fluoride compounds. Synthesis of rhenium, osmium, and iridium pentafluorides and tetrafluorides

Investigation of Molecular Iridium Fluorides IrFn (n=1–6): A Combined Matrix‐Isolation and Quantum‐Chemical Study

“…Previously the visible spectra of IrF 5 in HF solution were reported with two absorption bands at 683 and 840 nm [14c] . Later, the diffuse reflectance UV‐vis spectrum for solid IrF 5 with strong absorption bands in a broad range from about 200 to 500 nm, 840, and 1524 nm and similarly for IrF 3 at 256, 300, and 500 nm were published [14d,j] .…”

“…A systematic investigation that considers all possible iridium fluoride species is still lacking in the literature. IrF 5 was studied in the gas‐phase by mass spectrometry as well as in the solid state by X‐ray diffraction, infrared and Raman spectroscopy, diffuse reflectance UV‐vis spectroscopy and magnetic susceptibility measurements [14b–d] . On the other hand, only the solid‐state data were reported for IrF 4 [14c,f,g,h] and IrF 3 [14i,j] .…”

“…IrF 5 was studied in the gas‐phase by mass spectrometry as well as in the solid state by X‐ray diffraction, infrared and Raman spectroscopy, diffuse reflectance UV‐vis spectroscopy and magnetic susceptibility measurements [14b–d] . On the other hand, only the solid‐state data were reported for IrF 4 [14c,f,g,h] and IrF 3 [14i,j] . To the best of our knowledge, molecular IrF 2 has not yet been studied spectroscopically, nor is its solid‐state structure known.…”

Exploring the Limits of Transition‐Metal Fluorination at High Pressures

“…The first noble‐gas compounds, XeF 2 , XeF 4 and what was likely salts containing XeF n + cations, were, for example, either made through electric discharges of xenon and a fluorine source or through oxidation of xenon with PtF 6 . Transition‐metal fluorides can also be used as fluorination agents and as precursors to obtain various other compounds . For instance, MoF 6 is able to catalyze the fluorination of carbonyl groups to CF 2 groups .…”

“…[8,11,12] Transition-metal fluorides can also be used as fluorination agents and as precursors to obtain various other compounds. [13] Fori nstance,M oF 6 is able to catalyze the fluorination of carbonyl groups to CF 2 groups. [14,15] The synthesis of fluorides, [16,17] oxides,a nd oxofluorides, [18,19] can also be valuable for advancing our understanding of chemical bonding and chemical concepts, [3,4] for example,f or pushing the limits of the maximally reachable oxidation states of atoms.…”