Tetramethylammonium tetraiodopentabromide [NMe ][I Br ] was the first iodobromide to be synthesized and crystallized in an ionic liquid as well as in dichloromethane. The new iodobromides show different structure motives yet are unknown from other nonahalides and can be better described as [(I Br ) ⋅2 IBr]. The additional IBr units are connected by halogen-halogen interactions on the central V-shaped [I Br ] . The characterization was performed by Raman spectroscopy and single crystal X-ray structure determination. Conductivity measurements, thermogravimetric analysis and quantum-chemical calculations completed the structural discussion.

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.

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.

A facile one‐pot gram‐scale synthesis of tetraalkylammonium tetrafluoridochlorate(III) [cat][ClF4] ([cat]=[NEt3Me]+, [NEt4]+) is described. An acetonitrile solution of the corresponding alkylammonium chloride salt is fluorinated with diluted fluorine at low temperatures. The reaction proceeds via the [ClF2]− anion which is structurally characterized for the first time. The potential application of [ClF4]− salts as fluorinating agents is evaluated by the reaction with diphenyl disulfide, Ph2S2, to pentafluorosulfanyl benzene, PhSF5. The CN moieties in acetonitrile and [B(CN)4]− are transferred in CF3 groups. Exposure of carbon monoxide, CO, leads to the formation of carbonyl fluoride, COF2, and elemental gold is dissolved under the formation of tetrafluoridoaurate [AuF4]−.

Chlorine plays a central role for the industrial production of numerous materials with global relevance. More recently, polychlorides have been evolved from an area of academic interest to a research topic with enormous industrial potential. In this minireview, the value of trichlorides for chlorine storage and chlorination reactions are outlined. Particularly, the inexpensive ionic liquid [NEt 3 Me][Cl 3 ] shows a similar and sometimes even advantageous reactivity compared to chlorine gas, while offering a superior safety profile. Used as a chlorine storage, [NEt 3 Me][Cl 3 ] could help to overcome the current limitations of storing and transporting chlorine in larger quantities. Thus, trichlorides could become a key technique for the flexibilization of the chlorine production enabling an exploitation of renewable, yet fluctuating, electrical energy. As the loaded storage, [NEt 3 Me][Cl 3 ], is a proven chlorination reagent, it could directly be employed for downstream processes, paving the path to a more practical and safer chlorine industry.

Herein we report the synthesis and structural characterization of four novel polychloride compounds. The compounds [CCl(NMe2)2][Cl(Cl2)3] and [NPr4][Cl(Cl2)4] have been obtained from the reaction of the corresponding chloride salts with elemental chlorine at low temperature. They are the missing links in the series of polychloride monoanions [Cl(Cl)n]− (n=1–6). Additionally, the reaction of decamethylferrocene with elemental chlorine was studied yielding [Cp*2Fe]2[Cl20], which contains the largest known polychloride [Cl20]2− to date, and [Cp*2Fe][Cl(Cl2)4(HF)], which is the first example of a polychloride‐HF network stabilized by strong hydrogen and halogen bonding. All compounds have been characterized by single‐crystal X‐ray diffraction, Raman spectroscopy and quantum‐chemical calculations.

The use of neat BrCl in organic and inorganic chemistry is limited due to its gaseous aggregate state and especially its decomposition into Cl 2 andB r 2 .T he stabilization of BrCl in form of reactive ionic liquidsv ia an ovel in situ synthesis route shifts this equilibrium drastically to the BrCl side, which leads to safer and easier-to-handle interha-logenation reagents. Furthermore, the crystallined erivatives of the hitherto unknown [Cl(BrCl) 2 ] À and [Cl(BrCl) 4 ] À anions were synthesized and characterized by single-crystal X-ray diffraction (XRD), Ramana nd IR spectroscopy,a sw ell as quantum chemical calculations.

A new synthetic access to the Lewis acid [Au(OTeF5)3] and the preparation of the related, unprecedented anion [Au(OTeF5)4]− with inorganic or organic cations starting from commercially available and easy‐to‐handle gold chlorides are presented. In this first extensive study of the Lewis acidity of a transition‐metal teflate complex by using different experimental and quantum chemical methods, [Au(OTeF5)3] was classified as a Lewis superacid. The solid‐state structure of the triphenylphosphine oxide adduct [Au(OPPh3)(OTeF5)3] was determined, representing the first structural characterization of an adduct of this highly reactive [Au(OTeF5)3]. Therein, the coordination environment around the gold center slightly deviates from the typical square planar geometry. The [Au(OTeF5)4]− anion shows a similar coordination motif.