dc.contributor.author |
Casadevall, Carla |
dc.contributor.author |
Martin-Diaconescu, Vlad |
dc.contributor.author |
Browne, Wesley R. |
dc.contributor.author |
Fernández, Sergio |
dc.contributor.author |
Franco, Federico |
dc.contributor.author |
Cabello, Noemí |
dc.contributor.author |
Benet-Buchholz, Jordi |
dc.contributor.author |
Lassalle-Kaiser, Benedikt |
dc.contributor.author |
Lloret-Fillol, Julio |
dc.date.accessioned |
2023-05-15T09:11:37Z |
dc.date.available |
2023-05-15T09:11:37Z |
dc.date.issued |
2021-05-31 |
dc.identifier.uri |
http://hdl.handle.net/2072/534379 |
dc.format.extent |
6 p. |
dc.language.iso |
eng |
dc.publisher |
Springer Nature |
dc.rights |
Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 (CC BY-NC-ND) License |
dc.source |
RECERCAT (Dipòsit de la Recerca de Catalunya) |
dc.subject.other |
Química |
dc.title |
Isolation of a Ru(iv) side-on peroxo intermediate in the water oxidation reaction |
dc.type |
info:eu-repo/semantics/article |
dc.type |
info:eu-repo/semantics/acceptedVersion |
dc.subject.udc |
00 - Ciència i coneixement. Investigació. Cultura. Humanitats |
dc.embargo.terms |
6 mesos |
dc.relation.projectID |
ICIQ Foundation |
dc.relation.projectID |
MEC for PhD grants FPU14/02550 (C.C.) and FPU16/04234 (S.F.), and for the AP2Chem project (Ref: PID2019-110050RB-I00) |
dc.relation.projectID |
European Research Foundation for project FP7-PEOPLE-2010-ERG-268445 |
dc.relation.projectID |
CELLEX Foundation through the CELLEX-ICIQ high-throughput experimentation platform, |
dc.relation.projectID |
Netherlands Ministry of Education, Culture and Science (Gravity Program 024.001.035, W.R.B.) |
dc.identifier.doi |
10.1038/s41557-021-00702-5 |
dc.rights.accessLevel |
info:eu-repo/semantics/openAccess |
dc.description.abstract |
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. |