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• W2000664230 endingPage "13704" @default.
• W2000664230 startingPage "13694" @default.
• W2000664230 abstract "To examine the real ability of the binuclear di-mu-oxo complex [Mn2(III,IV)O2(terpy)2(H2O)2]3+ (2) to act as a catalyst for water oxidation, we have investigated in detail its redox properties and that of its mononuclear precursor complex [Mn(II)(terpy)2]2+ (1) in aqueous solution. It appears that electrochemical oxidation of 1 allows the quantitative formation of 2 and, most importantly, that electrochemical oxidation of 2 quantitatively yields the stable tetranuclear Mn(IV) complex, [Mn4(IV)O5(terpy)4(H2O)2]6+ (4), having a linear mono-mu-oxo{Mn2(mu-oxo)2}2 core. Therefore, these results show that the electrochemical oxidation of 2 in aqueous solution is only a one-electron process leading to 4 via the formation of a mono-mu-oxo bridge between two oxidized [Mn2(IV,IV)O2(terpy)2(H2O)2]4+ species. 4 is also quantitatively formed by dissolution of the binuclear complex [Mn2(IV,IV)O2(terpy)2(SO4)2] (3) in aqueous solutions. Evidence of this work is that 4 is stable in aqueous solutions, and even if it is a good synthetic analogue of the dimers-of-dimers model compound of the OEC in PSII, this complex is not able to oxidize water. As a consequence, since 4 results from an one-electron oxidation of 2, 2 cannot act as an efficient homogeneous electrocatalyst for water oxidation. This work demonstrates that a simple oxidation of 2 cannot produce molecular oxygen without the help of an oxygen donor." @default.
• W2000664230 created "2016-06-24" @default.
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• W2000664230 date "2005-09-08" @default.
• W2000664230 modified "2023-10-17" @default.
• W2000664230 title "Electrochemical and Chemical Formation of [Mn₄^IVO₅(terpy)₄(H₂O)₂]⁶⁺, in Relation with the Photosystem II Oxygen-Evolving Center Model [Mn₂^III,IVO₂(terpy)₂(H₂O)₂]³⁺" @default.
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• W2000664230 doi "https://doi.org/10.1021/ja052595+" @default.
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