Reactions of thorium tetrahalides ThX4 (X=Cl, Br, I) with liquid ammonia at room temperature lead to the formation of decaammine thorium(IV) halide ammoniates. Their different compositions [Th(NH3)10]X4 ⋅ nNH3 were established by single crystal X‐ray diffraction. While for the chloride the formation of a tetraammoniate is observed, the reaction of the bromide leads to an octaammoniate, whereas the iodide results in approximately a nonaammoniate. Additionally, the formation of the dinuclear Th complex compound [Th2Cl2(NH3)14(μ‐O)]Cl4 ⋅ 3NH3 was observed when moisture was present within NH3. As expected, the Th and the previously reported U compounds [An(NH3)10]Br4 ⋅ 8NH3 (Pbca, An=Th, U), [An(NH3)10]I4 ⋅ 9NH3 (P4/n), and [An2Cl2(NH3)14(μ‐O)]Cl4 ⋅ 3NH3 (Ptrue1‾ ) are isotypic, respectively. Surprisingly, ThCl4 formed the decaammine complex [Th(NH3)10]Cl4 ⋅ 4NH3 (P121/n1), while UCl4 formed the octaammine chlorido complex [UCl(NH3)8]Cl3 ⋅ 3NH3 (Pnma) in ammonia. Quantum‐chemical gas‐phase calculations were carried out to study the molecular structures and the energetics of the complex cations. In addition, the localized molecular orbitals (LMO) and Intrinsic Bonding Orbitals (IBO) were analyzed. However, the calculations could not explain the preferred formation of the [Th(NH3)10]4+ complex over the hypothetical cation [ThCl(NH3)8]3+.

No abstract

During the production of commercial lithium-ion batteries, the solid electrolyte interphase (SEI) on the graphite particles of the negative electrode is typically formed through galvanostatic protocols with low current densities. Consequently, SEI formation is a time-consuming and rather expensive production step. In order to better understand the influence of the formation current density on the transport of ions and molecules across the SEI, we formed model-type SEIs on planar glassy carbon electrodes under galvanostatic control. In accordance with the expectations from electrochemical nucleation and growth theory, we find that the transport of both ions and molecule becomes slower with increasing formation current density. However, it is remarkable that the ion transport is slowed down more strongly than the molecule transport. We show that at high formation current densities of about À 71 μA cm À 2 , our model-type SEIs clearly exceed the area-specific resistance tolerable in commercial lithium-ion cells.

BrF 5 can be prepared by treating BrF 3 with fluorine under UV light in the region of 300 to 400 nm at room temperature. It was analyzed by UV-Vis, NMR, IR and Raman spectroscopy. Its crystal structure was redetermined by X-ray diffraction, and its space group was corrected to Pnma. Quantum-chemical calculations were performed for the band assignment of the vibrational spectra. A monoclinic polymorph of BrF 5 was quantum chemically predicted and then observed as its low-temperature modification in space group P2 1 /c by single crystal X-ray diffraction. BrF 5 reacts with the alkali metal fluorides AF (A = K, Rb) to form alkali metal hexafluoridobromates(V), A[BrF 6 ] the crystal structures of which have been determined. Both compounds crystallize in the K[AsF 6 ] structure type (R � 3, no. 148, hR24). For the species [BrF 6 ] + , BrF 5 , [BrF 6 ] À , and [IF 6 ] À , the chemical bonds and lone pairs on the heavy atoms were investigated by means of intrinsic bond orbital analysis.

We investigated whether [SiF4(NH3)2] can act as a fluoride-ion acceptor in its reactions with the fluorides AF (A = Li–Cs, Tl, NH4) in anhydrous liquid ammonia (NH3). While LiF and NaF did not react, we obtained the compounds K­[SiF5(NH3)], Rb­[SiF5(NH3)], and Cs­[SiF5(NH3)], as well as [NH4(NH3)2]2[SiF6] and [Tl2(NH3)6]­[SiF6]·2NH3, from the other starting materials and characterized them by either single-crystal or powder X-ray diffraction. The compound [NH4(NH3)2]2[SiF6] contains the very rarely observed hydrogen-bonded, C 2v -symmetric diammine ammonium cation [NH4(NH3)2]+, and the compound [Tl2(NH3)6]­[SiF6]·2NH3 is an example for an uncommon Tl­(I)–Tl­(I) interaction. This “thallophilic” interaction was investigated with quantum-chemical methods.