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Chemistry ; 27(68): 17066-17077, 2021 Dec 06.
Artículo en Inglés | MEDLINE | ID: mdl-34643965

RESUMEN

Heuristic rules that allow identifying the preferred mixed-valence isomers and Jahn-Teller axis arrangements in the water oxidation catalyst [(Mn4 O4 )(V4 O13 )(OAc)3 ]n- and its activated form [(Mn4 O4 )(V4 O13 )(OAc)2 (H2 O)(OH)]n- are derived. These rules are based on computing all combinatorially possible mixed-valence isomers and Jahn-Teller axis arrangements of the MnIII atoms, and associate energetic costs with some structural features, like crossings of multiple Jahn-Teller axes, the location of these axes, or the involved ligands. It is found that the different oxidation states localize on different Mn centers, giving rise to clear Jahn-Teller distortions, unlike in previous crystallographic findings where an apparent valence delocalization was found. The low barriers that connect different Jahn-Teller axis arrangements suggest that the system quickly interconverts between them, leading to the observation of averaged bond lengths in the crystal structure. We conclude that the combination of cubane-vanadate bonds that are chemically inert, cubane-acetate/water bonds that can be activated through a Jahn-Teller axis, and low activation barriers for intramolecular rearrangement of the Jahn-Teller axes plays an essential role in the reactivity of this and probably related compounds.


Asunto(s)
Manganeso , Agua , Catálisis , Oxidación-Reducción , Vanadatos
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