Literature DB >> 24805267

Three H₂O₂ molecules are involved in the "Fenton-like" reaction between Co(H₂O)₆²⁺ and H₂O₂.

Ariela Burg1, Inna Shusterman, Haya Kornweitz, Dan Meyerstein.   

Abstract

Co(II) complexes and Co(H2O)6(2+) are used as catalysts in advanced oxidation processes. Therefore it was decided to study the kinetics of reaction of Co(H2O)6(2+) with H2O2. Surprisingly, the kinetic results point out that the process involves three consecutive reactions, each of them requiring an H2O2 molecule, i.e. three H2O2 molecules ligate to the central cobalt cation prior to the formation of radicals. DFT analysis suggests that the transient (H2O)3Co(II)(OOH)2(H2O2) decomposes via: (H2O)3Co(II)(OOH)2(H2O2) → (H2O)3Co(II)(OOH)(˙OOH)(OH) + ˙OH ΔG(0) = -5.975 kcal mol(-1), with no evidence for the formation of a Co(III) transient. It is proposed that analogous mechanisms are involved whenever the redox potential of the central cation is too high to enable the reaction: M(H2O)6(n+) + H2O2 → M((n+1)+)aq + ˙OH + OH(-).

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Year:  2014        PMID: 24805267     DOI: 10.1039/c4dt00401a

Source DB:  PubMed          Journal:  Dalton Trans        ISSN: 1477-9226            Impact factor:   4.390


  3 in total

1.  Amine oxidative N-dealkylation via cupric hydroperoxide Cu-OOH homolytic cleavage followed by site-specific fenton chemistry.

Authors:  Sunghee Kim; Jake W Ginsbach; Jung Yoon Lee; Ryan L Peterson; Jeffrey J Liu; Maxime A Siegler; Amy A Sarjeant; Edward I Solomon; Kenneth D Karlin
Journal:  J Am Chem Soc       Date:  2015-02-23       Impact factor: 15.419

Review 2.  What Are the Oxidizing Intermediates in the Fenton and Fenton-like Reactions? A Perspective.

Authors:  Dan Meyerstein
Journal:  Antioxidants (Basel)       Date:  2022-07-14

3.  The Role of Carbonate in Catalytic Oxidations.

Authors:  Shanti Gopal Patra; Amir Mizrahi; Dan Meyerstein
Journal:  Acc Chem Res       Date:  2020-09-25       Impact factor: 22.384

  3 in total

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