Herein, we report the use of alkyl ammonium chloride salts as safe and sustainable chlorine storage media. The most promising candidate, [NEt3Me]­Cl, stores up to 0.79 kg chlorine/kg storage material, is readily prepared, and stable against chlorination for extended times. Chlorine release can be achieved by applying heat or vacuum, or, alternatively, by the addition of water. The combination of these properties emphasizes [NEt3Me]Cl as a suitable storage medium to facilitate the flexibilization of industrial chlorine production. As polychlorides can be used for various chlorination reactions, a combined industrial process is envisaged utilizing [NEt3Me]Cl as the storage medium and the loaded system, [NEt3Me]­[Cl­(Cl2) n ] (n = 1.68), as the reagent for industrial chlorinations.

The synthesis of anionic chalcogenidometalate superspheres can be achieved from [Ge Se ] salts and SnCl in ionic liquids with 1-alkyl-(2,)3-(di)methylimidazolium cations, denoted as (C (C )C Im) (alkyl = butyl for n=4, hexyl for n=6, octyl for n=8). Their formation is apparently independent from the lengths of the C chain, and the presence or absence of a second methyl group at the ionic liquid cation (that are exchanged for alkali metal cations in precursor compounds during the reactions), although this may appear counterintuitive. In contrast, and equally counterintuitive, the ionic liquid anion was found to play a crucial role for both the general observability as well as the crystal yield and quality of the products, although they are not part of the product: a minimum content of chloride is needed, while ionic liquids with [BF ] anions alone do not support the product formation/crystallization. The observation suggests a subtle equilibrium of SnCl with according halidostannate anions that decreases the reactivity of the tin source. The finding is of particular interest, as chloride anions were shown to have been major impurities of former "chloride-free" ionic liquid charges, which potentially led to irreproducible synthesis protocols in the literature.

Chloride ions are efficient catalysts for the synthesis of phosgene from carbon monoxide and elemental chlorine at room temperature and atmospheric pressure. Control experiments rule out a radical mechanism and highlight the role of triethylmethylammonium trichloride, [NEt 3 Me][Cl 3 ], as active species. In the catalytic reaction, commercially available [NEt 3 Me]Cl reacts with Cl 2 to form [NEt 3 Me][Cl 3 ], enabling the insertion of CO into an activated Cl─Cl bond with a calculated energy barrier of 56.9 to 77.6 kJ mol −1 . As [NEt 3 Me]Cl is also a useful chlorine storage medium, it could serve as a catalyst for phosgene production and as chlorine storage in a combined industrial process.

Metal clusters featuring carbon and sulfur donors have coordination environments comparable to the active site of nitrogenase enzymes. Here, we report a series of di-iron clusters supported by the dianionic yldiide ligands, in which the Fe sites are bridged by two μ 2 -C atoms and four pendant S donors.The [L 2 Fe 2 ] (L = {[Ph 2 P(S)] 2 C} 2− ) cluster is isolable in two oxidation levels, all-ferrous Fe 2 II and mixed-valence Fe II Fe III . The mixed-valence cluster displays two peaks in the Mossbauer spectra, indicating slow electron transfer between the two sites. The addition of the Lewis base 4-dimethylaminopyridine to the Fe 2 II cluster results in coordination with only one of the two Fe sites, even in the presence of an excess base. Conversely, the cluster reacts with 8 equiv of isocyanide t BuNC to give a monometallic complex featuring a new C−C bond between the ligand backbone and the isocyanide. The electronic structure descriptions of these complexes are further supported by X-ray absorption and resonant X-ray emission spectroscopies.

A high-yielding and facile synthesis for diphosphane monochalcogenides (1(Ch)((R))) and their constitutional isomers, diphosphanylchalcoganes (2(Ch)((R))), was developed, featuring a condensation reaction between chlorophosphanes (R2PCl) and sodium chalcogenides (Na2Ch, Ch = S, Se, (Te)). The optimized protocol selectively yields either 1(Ch)((R)) (R2(Ch)PPR2) or 2(Ch)((R)) (Ch(PR2)2) depending upon the steric demand of the substituents R. Reaction pathways consistent with the distinct reaction outcomes are proposed. The application of 1(Ch)((R)) and 2(Ch)((R)) as an interesting class of ligands is exemplarily demonstrated by the preparation of selected transition metal complexes.