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dc.contributor.authorAlmenara Pérez, Naroa
dc.contributor.authorGarralda Hualde, María Angeles ORCID
dc.contributor.authorLópez de Pariza Sanz, Xabier
dc.contributor.authorMatxain Beraza, Jon Mattin
dc.contributor.authorFreixa Fernández, Zoraida ORCID
dc.contributor.authorHuertos Mansilla, Miguel Angel ORCID
dc.date.accessioned2022-09-08T08:41:29Z
dc.date.available2022-09-08T08:41:29Z
dc.date.issued2022-09-05
dc.identifier.citationAngewandte Chemie International Edition 61(36) : (2022) // Article ID e202204558es_ES
dc.identifier.issn1433-7851
dc.identifier.issn1521-3773
dc.identifier.urihttp://hdl.handle.net/10810/57487
dc.description.abstract[EN] An unprecedented quantum tunneling effect has been observed in catalytic Si-H bond activations at room temperature. The cationic hydrido-silyl-iridium(III) complex, {Ir[SiMe(o-C6H4SMe)(2)](H)(PPh3)(THF)}[BAr4F], has proven to be a highly efficient catalyst for the hydrolysis and the alcoholysis of organosilanes. When triethylsilane was used as a substrate, the system revealed the largest kinetic isotopic effect (KIESi-H/Si-D=346 +/- 4) ever reported for this type of reaction. This unexpectedly high KIE, measured at room temperature, together with the calculated Arrhenius preexponential factor ratio (A(H)/A(D)=0.0004) and difference in the observed activation energy [(EaD -EaH )=34.07 kJ mol(-1)] are consistent with the participation of quantum tunneling in the catalytic process. DFT calculations have been used to unravel the reaction pathway and identify the rate-determining step. Aditionally, isotopic effects were considered by different methods, and tunneling effects have been calculated to be crucial in the process.es_ES
dc.description.sponsorshipThis research was supported by the Universidad del Pais Vasco (UPV/EHU) (GIU13/06), Ministerio de Economia y Competitividad (PID2019-111281GB-00), Gobierno Vasco (IT1880-19 and IT1254-19). Technical and human support provided by IZO-SGI, SGIKER (UPV/EHU, MICINN, GV/EJERDF and ESF), is gratefully acknowledged for assistance and generous allocation of computational resources. N.A. is grateful to Diputacion Foral de Gipuzkoa (OF215/2016), and M.A.H. and Z.F. to IKERBASQUE for funding. We would like to thank Dr. Eugene E. Kwan for his support and fruitful discussion using PyQuiver program.es_ES
dc.language.isoenges_ES
dc.publisherWileyes_ES
dc.relationinfo:eu-repo/grantAgreement/MICINN/PID2019-111281GB-I00es_ES
dc.rightsinfo:eu-repo/semantics/openAccesses_ES
dc.rights.urihttp://creativecommons.org/licenses/by/3.0/es/*
dc.subjecthomogeneous catalysises_ES
dc.subjectiridiumes_ES
dc.subjectquantum tunnelinges_ES
dc.subjectsilaneses_ES
dc.titleHydrogen Tunneling in Catalytic Hydrolysis and Alcoholysis of Silaneses_ES
dc.typeinfo:eu-repo/semantics/articlees_ES
dc.rights.holder© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.es_ES
dc.rights.holderAtribución 3.0 España*
dc.relation.publisherversionhttps://onlinelibrary.wiley.com/doi/10.1002/anie.202204558es_ES
dc.identifier.doi10.1002/anie.202204558
dc.departamentoesPolímeros y Materiales Avanzados: Física, Química y Tecnologíaes_ES
dc.departamentoesQuímica aplicadaes_ES
dc.departamentoeuPolimero eta Material Aurreratuak: Fisika, Kimika eta Teknologiaes_ES
dc.departamentoeuKimika aplikatuaes_ES


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© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Except where otherwise noted, this item's license is described as © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.