A Matrix‐Isolation and Quantum‐Chemical Investigation of FeF₄

Abstract

Jenseits von Eisentrifluorid: Matrixisolations‐IR‐Spektroskopie und hochgenaue quantenchemische Rechnungen ermöglichten die Charakterisierung von Eisentetrafluorid, einer bislang unbekannten Spezies. FeF4 wurde bei kryogenen Temperaturen durch Coabscheidung von Fluor und mithilfe von Laserstrahlung verdampften Eisenatomen in Gegenwart von Edelgasen (Neon und Argon) im Überschuss erhalten.

Searching for Monomeric Nickel Tetrafluoride: Unravelling Infrared Matrix Isolation Spectra of Higher Nickel Fluorides

“…A comparison of experimental M À F stretching bands of high-valent first-row metal fluorides is particularly revealing. The molecular trifluorides of M = Fe, Co, and Ni all adopt D 3h structures, and their stretching fundamentals were found in Ne matrices, in a very narrow range, at 743.6 cm À1 (Fe), [13] 748.2 cm À1 (Co), and 743.8 cm À1 (Ni, Table 1). For a series of molecules with similar structures one expects a strong correlation between stretching frequencies and bond lengths, a trend that also applies to the bond length of CoF 3 (1.722 ) and NiF 3 (1.722 , Table S3.5) obtained at the CCSD(T)/AVTZ level.…”

“…[2] In contrast to solid MnF 4 and NiF 4 , solid FeF 4 or solid CoF 4 are unknown, while the monomeric FeF 4 and CoF 4 species have been investigated by high-temperature vapor-phase mass spectrometry and cryogenic matrix-isolation spectroscopy. [11][12][13] Solid NiF 4 is one of the strongest known fluorinating oxidizing agents, [2] but it is poorly characterized spectroscopically and even its solid-state structure is unknown. We have not found any report on molecular or gaseous NiF 4 .…”

“…This method is particularly useful for the generation of highly fluorinated species. [13,19] For example, laser ablation from a metallic cobalt target in a fluorine/argon gas mixture clearly produces not only molecular CoF, CoF 2 and CoF 3 but also CoF 4 (for experimental details see the Supporting Information), which could be detected using its known IR band in solid argon reported in a previous study, [12] in which CoF 4 was obtained at 650 K from solid mixtures of CoF 3 and TbF 4 as atomic fluorine source in a perfluorinated nickel effusion cell. [12] The wavenumber ordering of the n Co-F modes is CoF 4 > CoF 3 > CoF 2 @ CoF, see the Supporting Information.…”

Helene Lange Prize: M. Schnell / International Young Talent Award in Fluorine Chemistry: S. Riedel / Roy L. Whistler International Award: G.‐J. Boons

“…Riedel’s research interests include the prediction and synthesis of main‐group and transition‐metal fluorides and oxyfluorides, f‐block compounds, polyhalogen anions, and weakly coordinating anions. Riedel was awarded the 2013 Publication Prize from the Fluorine Group of the Gesellschaft Deutscher Chemiker (GDCh; German Chemical Society) for his report in Angewandte Chemie on a matrix isolation and quantum‐chemical invesitgation of FeF 4 2a. He has also recently reported in Angewandte Chemie on evidence for the [Br 11 ] − ion 2b…”

Helene‐Lange‐Preis: M. Schnell / International Young Talent Award in Fluorine Chemistry: S. Riedel / Roy L. Whistler International Award: G.‐J. Boons

“…Zu seinen Forschungsinteressen zählt die Vorhersage und Synthese von Hauptgruppen‐ und Übergangsmetallfluoriden und ‐oxyfluoriden, f‐Block‐Verbindungen, Polyhalogenanionen und schwach koordinierenden Anionen. 2013 erhielt er den Publikationspreis der Arbeitsgemeinschaft Fluorchemie der Gesellschaft Deutscher Chemiker für seine Veröffentlichung in der Angewandten Chemie über die Matrixisolierung und quantenchemische Untersuchung von FeF 4 2a. Vor kurzem hat er außerdem in der Angewandten Chemie über Belege für das Ion [Br 11 ] − berichtet 2b…”