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Mechanism of Water Oxidation Catalyzed by a Mononuclear Manganese Complex
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Number of Authors: 4
2017 (English)In: ChemSusChem, ISSN 1864-5631, E-ISSN 1864-564X, Vol. 10, no 5, 903-911 p.Article in journal (Refereed) Published
Abstract [en]

The design and synthesis of biomimetic Mn complexes to catalyze oxygen evolution is a very appealing goal because water oxidation in nature employs a Mn complex. Recently, the mononuclear Mn complex [LMnII(H2O)(2)](2+) [1, L=Py2N(tBu)(2), Py= pyridyl] was reported to catalyze water oxidation electro-chemically at an applied potential of 1.23 V at pH 12.2 in aqueous solution. Density functional calculations were performed to elucidate the mechanism of water oxidation promoted by this catalyst. The calculations showed that 1 can lose two protons and one electron readily to produce [LMnIII(OH)(2)](+) (2), which then undergoes two sequential proton-coupled electron-transfer processes to afford [(LMnOO)-O-V](+) (4). The O-O bond formation can occur through direct coupling of the two oxido ligands or through nucleophilic attack of water. These two mechanisms have similar barriers of approximately 17 kcal mol(-1). The further oxidation of 4 to generate [(LMnO)-O-VI-O](2+) (5), which enables O-O bond formation, has a much higher barrier. In addition, ligand degradation by C-H activation has a similar barrier to that for the O-O bond formation, and this explains the relatively low turnover number of this catalyst.

Place, publisher, year, edition, pages
2017. Vol. 10, no 5, 903-911 p.
Keyword [en]
density functional theory, manganese, oxidation, reaction mechanism, water splitting
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-142672DOI: 10.1002/cssc.201601538ISI: 000398182300012PubMedID: 27925413OAI: oai:DiVA.org:su-142672DiVA: diva2:1094657
Available from: 2017-05-10 Created: 2017-05-10 Last updated: 2017-05-10Bibliographically approved

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