A Matrix‐Isolation and Quantum‐Chemical Investigation of FeF₄

Abstract

This work has been supported by the DFG project HA 5639/3-1 and the Fonds der Chemischen Industrie (FCI). We are grateful to the BWGrid cluster for providing computational resources and to Dr. Eicher from the Solvay Fluor GmbH for generous support with F 2 . We thank C. Roll, R. Tomm, and M. Melder from the technical workshop of the chemistry department for their help with the construction of the matrix chamber and the laser-ablation setup. We are also grateful to Prof. Ingo Krossing and Prof. Harald Hillebrecht for their generous and continuous support.Supporting information for this article is available on the WWW under http://dx.

A Stable Homoleptic Organometallic Iron(IV) Complex

“…Examples of Fe IV coordination compounds without stabilizing PDALs are scarce however. Besides FeF 4 , that could be isolated in a matrix, there are only few examples of more traditional Werner complexes using for example, electron‐donating dithiocarbamate ligands to stabilize the iron center in oxidation state Fe IV , or Fe IV complexes containing multidentate macrocyclic tetraamide ligands, a Fe IV cyclam–azide complex and a Fe IV cyano‐complex based on a tridentate imino‐ligand, the two latter electrochemically generated and studied in situ. To date, the exceptional example of an entirely stable Fe IV complex belongs to the class of coordination cage compounds; Fe IV hexahydrazide clathrochelate .…”

Recent Discoveries of Polyhalogen Anions – from Bromine to Fluorine

“…In contrast to the above discussed alkali trifluorides, which show an absorption at 550 cm –1 that is typical for cation‐anion complexes, the isolated trifluoride shows IR bands at 510.6 cm –1 and 524.7 cm –1 in argon and neon matrixes, respectively. To this day the isolated trifluoride has regularly been observed in matrix‐isolation experiments with laser‐ablated metals 82,83. A precise description of [F 3 ] – by quantum‐chemical calculations is challenging and requires correlation methods like CCSD(T) 81,84.…”

Reaction of Laser-Ablated Uranium and Thorium Atoms with H2Se: A Rare Example of Selenium Multiple Bonding

“…28 Uranium or thorium atoms were co-deposited with the argon/hydrogen selenide mixture following laser ablation from solid metal. The 1064 nm fundamental of a Nd:YAG laser (Continuum, Minilite II, 10 Hz repetition rate and 6 ns pulse width, laser energy about 25−40 mJ/pulse) was focused onto the rotating metal target through a hole in the cold window.…”