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Proton coupled electron transfer reaction of phenols with excited state ruthenium(II) – polypyridyl complexes
Authors:K. Swarnalatha  E. Rajkumar  S. Rajagopal  R. Ramaraj  I. Sadhiya Banu  P. Ramamurthy
Affiliation:1. Department of Chemistry, Manomanium Sundaranar University, Tirunelveli, India;2. School of Chemistry, Madurai Kamaraj University, Madurai 625 021, India;3. Department of Inorganic Chemistry, University of Madras, Chennai 600 025, India
Abstract:The reaction of phenols with the excited state, *[Ru(bpy)3]2+ (E0 = 0.76 V) and *[Ru(H2dcbpy)3]2+, (dcbpy = 4,4′‐dicarboxy‐2,2′‐bipyridine) (E0 = 1.55 V vs. SCE) complexes in CH3CN has been studied by luminescence quenching technique and the quenching is dynamic. The formation of phenoxyl radical as a transient is confirmed by its characteristic absorption at 400 nm. The kq value is highly sensitive to the change of pH of the medium and ΔG0 of the reaction. Based on the treatment of kq data in terms of energetics of the reaction and pH of the medium, proton coupled electron transfer (PCET) mechanism has been proposed for the reaction. Copyright © 2010 John Wiley & Sons, Ltd.
Keywords:photooxidation of phenols  proton coupled electron transfer  Ru(II)‐polypyridyl complexes
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