Old City Publishing/De Gruyter
The photooxidation of ethylferrocene to ethylferricinium ion and tetrachloroferrate in CHCl3 under 254 nm irradiation proceeds through light absorption by both ethylferrocene and chloroform. The products remain in solution at concentrations below 10-3 M. The fraction occurring through a solvent-initiated pathway increases during the course of the reaction. A secondary thermal reaction is responsible for generating tetrachloroferrate from ethylferricinium ion. The rate of the reaction increases during the early stages, and the data throughout the course of the reaction are consistent with the rate law ( afs + bfR)/ (1 + c[R]/[P]-d[R]/[Cl ]), where [R] and [P] are the concentrations of ethylferrocene and ethylferricinium ion, respectively, and ƒs and ƒR are the fractions of light absorbed by the solvent and ethylferrocene, respectively.
Son L. Phan and Patrick E. Hoggard, "A kinetic study of the photolysis of ethylferrocene in chloroform", Inorg. React. Mech. 1, 17-24 (1998).