Títol:
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Isolation of a Ru(iv) side-on peroxo intermediate in the water oxidation reaction
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Autor/a:
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Casadevall, Carla; Martin-Diaconescu, Vlad; Browne, Wesley R.; Fernández, Sergio; Franco, Federico; Cabello, Noemí; Benet-Buchholz, Jordi; Lassalle-Kaiser, Benedikt; Lloret-Fillol, Julio
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Abstract:
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Oxygen-containing mononuclear ruthenium species such as ruthenium(III)-hydroxo, ruthenium(IV)-oxo, ruthenium(V)-oxo and ruthenium(IV)-peroxo are invoked as key intermediates in O-O bond formation during Ru catalyzed water oxidation. However, the extreme instability of these species, as a result of the high oxidation states of Ru, makes their isolation and study quite challenging. In particular, the nature of the putative peroxo species has been a topic of debate in the last decades and still remains unclear. Herein we report the isolation and full spectroscopic as well as crystallographic characterization of a Ru(IV) side-on peroxo complex, a key missing link after the rate-determining O-O bond formation. Experimental data coupled with theoretical calculations point to a peroxo moiety symmetrically coordinated to the Ru atom leading to a closed shell electronic structure for h2-[RuIV-OO]2+. Labeling studies evidence the direct evolution of O2 from the nucleophilic attack of a H2O molecule to the highly electrophilic Ru=O species via the formation of the h2-[RuIV-OO]2+ intermediate. |
Data de publicació:
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31-05-2021 |
Matèries (CDU):
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00 - Ciència i coneixement. Investigació. Cultura. Humanitats |
Matèries:
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Química |
Drets:
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Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 (CC BY-NC-ND) License |
Pàgines:
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6 p. |
Tipus de document:
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Article Article - Versió acceptada |
DOI:
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10.1038/s41557-021-00702-5
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Publicat per:
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Springer Nature
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Compartir:
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