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Dissolved hexachlororuthenate(IV) effectively catalyzes the photodecomposition of chloroform to hydrogen chloride and phosgene under near‐UV (λ > 345 nm) irradiation, whereby RuCl62− is not itself photocatalytically active, but is photochemically transformed into a species that is active, possibly RuCl5(CHCl3)−. Conversion to a photoactive species during irradiation is consistent with the acceleration...