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.
The preparation and structural characterization of [NEt3Me]2[SCl6] is described, which is the first example of a [SCl6]2− dianion and of a halosulfate anion of the type [SxXy]z− in general. This dianion belongs to the group of 14‐valence electron AB6E systems and forms an octahedral structure in the solid‐state. Interestingly, co‐crystallization with CH2Cl2 affords [NEt3Me]2[SCl6]⋅4 CH2Cl2 containing [SCl6]2− dianions with C4v symmetry. As suggested by quantum‐chemical calculations, the distortion of the structure is not caused by a stereochemically active lone pair but by enhanced hydrogen bonding interactions with CH2Cl2. At elevated temperatures, [NEt3Me]2[SCl6] decomposes to various sulfur chlorine compounds as shown by Raman spectroscopy. Cooling back to room temperature results in the selective formation of [NEt3Me]2[SCl6] which is comparable to the well‐studied SCl4.
Es wird über die Herstellung und strukturelle Charakterisierung von [NEt3Me]2[SCl6] berichtet. Diese Verbindung ist das erste Beispiel für ein [SCl6]2−‐Dianion und für ein Halogensulfat‐Anion vom Typ [SxXy]z− im Allgemeinen. Das [SCl6]2− gehört zur Gruppe der AB6E‐Systeme mit 14 Valenzelektronen und bildet im festen Zustand eine oktaedrische Struktur aus. Interessanterweise führt die Co‐Kristallisation von CH2Cl2 zur Bildung von [NEt3Me]2[SCl6]⋅4 CH2Cl2 in dem das [SCl6]2−‐Dianion eine C4v‐Symmetrie aufweist. Wie quantenchemische Berechnungen nahelegen, wird die Verzerrung der Struktur nicht durch ein stereochemisch aktives freies Elektronenpaar, sondern durch verstärkte Wasserstoffbrückenbindungen mit CH2Cl2 verursacht. Bei erhöhten Temperaturen zersetzt sich [NEt3Me]2[SCl6] in verschiedene Schwefel‐Chlor‐Verbindungen, wie sich durch Raman‐Spektroskopie nachweisen lässt. Abkühlen auf Raumtemperatur führt zur selektiven Bildung von [NEt3Me]2[SCl6], das mit dem gut untersuchten SCl4 vergleichbar ist.
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