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 of the decomposition rate during the early stages and with the apparent inverse dependence of the decomposition rate on the initial concentration of RuCl62−. The displacement of Cl− by CHCl3 in the coordination sphere to create the photoactive species is consistent with the retardation of photodecomposition by both Cl− and H2O. The much smaller photodecomposition rate in CDCl3 suggests that C–H bond dissociation occurs during the primary photochemical event, which is also consistent with the presence of a CHCl3 molecule in the first coordination sphere.
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