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, [NEtMe][Cl], as active species. In the catalytic reaction, commercially available [NEtMe]Cl reacts with Cl to form [NEtMe][Cl], enabling the insertion of CO into an activated Cl─Cl bond with a calculated energy barrier of 56.
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