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Abstract

Irradiation (λ > 320 nm) of ferrocene in chloroform causes decomposition of chloroform and the accumulation of HCl, CCl3OOH, and C2Cl6. This appears to occur initially through a cycle in which (a) ferrocene is oxidized to ferrocenium and tetrachloroferrate ions, (b) FeCl4 undergoes photodissociation, and (c) ferrocenium reoxidizes the chloroferrate(II) species. On extended photolysis, the concentrations of CCl3OOH and FeCl4 build up and a competing cycle in which FeCl4 is restored through oxidation of the chloroferrate(II) species by CCl3OOH accelerates the decomposition rate.

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