Effect of fluorine substitution on the √ OH-radical-induced electron-transfer reaction in aqueous solutions of fluorinated alkyl iodides

Mohan, Hari ; Maity, Dilip K. ; Mittal, Jai P. (1994) Effect of fluorine substitution on the √ OH-radical-induced electron-transfer reaction in aqueous solutions of fluorinated alkyl iodides Chemical Physics Letters, 220 (6). pp. 455-460. ISSN 0009-2614

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Official URL: http://linkinghub.elsevier.com/retrieve/pii/000926...

Related URL: http://dx.doi.org/10.1016/0009-2614(94)00197-9

Abstract

The transient optical absorption bands formed at λ max=340 and 435 nm, on reaction of √ OH radicals in aerated acidic aqueous solutions of 1,1,1-trifluoro-2-iodoethane at low and high solute concentration, have been assigned to monomer and dimer radical cations, respectively. The deprotonation of the solute radical cations is the rate-determining step for the decay of the dimer radical cations. The stability constant for the dimer radical cation is determined to be 50 dm3 mol-1 at 25 ° C. The dimer radical cation is a strong one-electron oxidant. Quantum chemical calculations and experimental results confirm that fluorine reduces the electron density at iodine and the √ OH-radical-induced oxidation of fluoroiodoalkanes becomes a difficult process compared to iodoalkanes.

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