Hydrogen Atom Transfer Thermodynamics of Homologous Co(III)- and Mn(III)-Superoxo Complexes: The Effect of the Metal Spin State.

ABSTRACT: Systematic investigations on H atom transfer (HAT) thermodynamics of metal O₂ adducts is of fundamental importance for the design of transition metal catalysts for substrate oxidation and/or oxygenation directly using O₂. Such work should help elucidate underlying electronic-structure features that govern the OO-H bond dissociation free energies (BDFEs) of metal-hydroperoxo species, which can be used to quantitatively appraise the HAT activity of the corresponding metal-superoxo complexes. Herein, the BDFEs of two homologous Co^III- and Mn^III-hydroperoxo complexes, 3-Co and 3-Mn, were calculated to be 79.3 and 81.5 kcal/mol, respectively, employing the Bordwell relationship based on experimentally determined pK _a va

SUBMITTER: Tian YC 

PROVIDER: S-EPMC9400055 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature