Photoinduced Electron Transfer in Donor-acceptor Complexes of Ethylene with Molecular and Atomic Iodine


Building upon our recent studies of radical addition pathways following excitation of the I2 chromophore in the donor-acceptor complex of ethylene and I2 (C2H4··· I2), in this article, we extend our studies to examine photoinduced electron transfer. Thus, irradiation into the intense charge-transfer band of the complex (λmax = 247 nm) gave rise to a band at 366 nm that is assigned to the bridged ethylene-I radical complex on the basis of our prior work. the formation of the radical complex is explained by a mechanism that involves rapid back electron transfer leading to I-I bond fission. Excitation into the charge-transfer band of the radical complex led to regeneration of the parent complex and the formation of the final photoproduct, anti- and gauche-1,2-diiodoethane, which confirms that the reaction proceeds ultimately by a radical addition mechanism. This finding is contrasted with our previous study of the C2H4···Br2 complex, where CT excitation led to only one product, anti-1,2-dibromoethane, a result explained by a single electron-transfer mechanism proceeding via a bridged bromonium ion intermediate. For the I2 complex, the breakup of the photolytically generated I2 anion radical is apparently sufficiently slow to render it uncompetitive with back electron transfer. Finally, we report a detailed computational examination of the parent and radical complexes of both bromine and iodine, using high-level single- and multireference methods, which provide insight into the different behaviors of the charge-transfer states of the two radicals and the role of spin-orbit coupling. © 2014 American Chemical Society.



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