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.

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.