Abstract
The electronic spectrum of the diperoxo complex MeReVII(O-2)(2)O shows a peroxide IL (intraligand) absorption at lambda(max) similar to 260 nm in addition to the well-known peroxide to Re(VII) LMCT band at lambda(max) = 358 nm. Upon IL excitation, the diperoxo group undergoes a dismutation. Accordingly, MeRe(O-2)(2)O Photolyzes to (MeReO3)-O-VII and O-2. LMCT excitation at lambda(irr) = 405 nm is ...
Abstract
The electronic spectrum of the diperoxo complex MeReVII(O-2)(2)O shows a peroxide IL (intraligand) absorption at lambda(max) similar to 260 nm in addition to the well-known peroxide to Re(VII) LMCT band at lambda(max) = 358 nm. Upon IL excitation, the diperoxo group undergoes a dismutation. Accordingly, MeRe(O-2)(2)O Photolyzes to (MeReO3)-O-VII and O-2. LMCT excitation at lambda(irr) = 405 nm is assumed to generate the radical pair MeReVII(O-2)O+/O-2(-) in the primary photochemical step. Back electron transfer and reaction with water leads finally to the monoperoxo complex MeReVII(O-2)O-2 and H2O2. (c) 2005 Elsevier B.V. All rights reserved.
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