Superoxo, Peroxo, and Hydroperoxo Complexes Formed from Reactions of Rhodium Porphyrins with Dioxygen: Thermodynamics and Kinetics
- 22 July 2006
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 128 (32), 10350-10351
- https://doi.org/10.1021/ja0628755
Abstract
Rhodium(II) porphyrin complexes react with dioxygen to form terminal superoxo and bridged mu-peroxo complexes. Equilibrium constants for dioxygen complex formation with rhodium(II) tetramesitylporphyrin ((TMP)Rh*) and a m-xylyl-tethered dirhodium(II) diporphyrin complex (*Rh(m-xylyl)Rh*) are reported. (TMP)Rh-H reacts with oxygen to form a transient hydroperoxy complex ((TMP)Rh-OOH), which reacts on to form the rhodium(II) complex ((TMP)Rh*) and water. Kinetic studies for reactions of (TMP)Rh-H with O2 suggest a near concerted addition of dioxygen to the (TMP)Rh-H unit. Reactivity studies for mixtures of H2/O2 and CH4/O2 with the dirhodium(II) complex (*Rh(m-xylyl)Rh*) are reported.Keywords
This publication has 11 references indexed in Scilit:
- Copper(II) catalyzed selective oxidation of primary alcohols to aldehydes with atmospheric oxygenTetrahedron Letters, 2005
- Recent Advances in Transition Metal Catalyzed Oxidation of Organic Substrates with Molecular OxygenChemical Reviews, 2005
- Green, Catalytic Oxidations of AlcoholsAccounts of Chemical Research, 2002
- Structural and Mechanistic Investigations of the Oxidation of Dimethylplatinum(II) Complexes by DioxygenInorganic Chemistry, 2002
- Kinetics and Thermodynamics of Hydrogen Atom Transfer to Superoxometal ComplexesJournal of the American Chemical Society, 1997
- Reactions of hydrogen or deuterium molecule with a rhodium(II) metalloradical: kinetic evidence for a four-centered transition stateInorganic Chemistry, 1992
- Selective catalytic oxidation using hydrogen/oxygen mixtures with solutions of iridium and rhodium complexesCanadian Journal of Chemistry, 1983
- Dioxygen complexes of rhodium porphyrinsJournal of the American Chemical Society, 1979
- Photoinduced oxygenation of trans-aquohydridotetraamminerhodium(III). Evidence for a transition-metal chain carrierInorganic Chemistry, 1979
- Catalysis by cobalto-cyano complexes in non-aqueous solventsDiscussions of the Faraday Society, 1968