Inorg. Chem. 2002, 41, 3975−3982
Generation and Reactivity of Rhodium(IV) Complexes in Aqueous Solutions Oleg Pestovsky and Andreja Bakac* Ames Laboratory, Iowa State UniVersity of Science and Technology, Ames, Iowa 50011 Received April 9, 2002
At pH ) 1 and 25 °C, the Fenton-like reactions of Feaq2+ with hydroperoxorhodium complexes LRhIIIOOH2+ (L ) (H2O)(NH3)4, k ) 30 M-1 s-1, and L ) L2 ) (H2O)(meso-Me6-[14]aneN4), k ) 31 M-1 s-1) generate short-lived, reactive intermediates, believed to be the rhodium(IV) species LRhIVO2+. In the rapid follow-up steps, these transients oxidize Feaq2+, and the overall reaction has the standard 2:1 [Feaq2+]/[LRhOOH2+] stoichiometry. Added substrates, such as alcohols, aldehydes, and (NH3)4(H2O)RhH2+, compete with Feaq2+ for LRhIVO2+, causing the stoichiometry to change to
