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Mechanism of Water ...
Mechanism of Water Oxidation Catalyzed by a Mononuclear Manganese Complex
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Li, Ying-Ying (författare)
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Ye, Ke (författare)
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- Siegbahn, Per E. M. (författare)
- Stockholms universitet,Institutionen för organisk kemi
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Liao, Rong-Zhen (författare)
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(creator_code:org_t)
- 2017-02-14
- 2017
- Engelska.
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Ingår i: ChemSusChem. - : Wiley. - 1864-5631 .- 1864-564X. ; 10:5, s. 903-911
- Relaterad länk:
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
Ämnesord
Stäng
- 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.
Ämnesord
- NATURVETENSKAP -- Kemi -- Organisk kemi (hsv//swe)
- NATURAL SCIENCES -- Chemical Sciences -- Organic Chemistry (hsv//eng)
Nyckelord
- density functional theory
- manganese
- oxidation
- reaction mechanism
- water splitting
Publikations- och innehållstyp
- ref (ämneskategori)
- art (ämneskategori)
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