Please use this identifier to cite or link to this item: http://hdl.handle.net/10316/91165
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dc.contributor.authorNunes, C. M.-
dc.contributor.authorViegas, Luís P.-
dc.contributor.authorWood, Samuel A-
dc.contributor.authorRoque, José P L-
dc.contributor.authorMcMahon, Robert J-
dc.contributor.authorRui Fausto-
dc.date.accessioned2020-10-10T16:49:25Z-
dc.date.available2020-10-10T16:49:25Z-
dc.date.issued2020-06-17-
dc.identifier.issn1433-7851pt
dc.identifier.issn1521-3773pt
dc.identifier.urihttp://hdl.handle.net/10316/91165-
dc.description.abstractNot long ago, the occurrence of quantum mechanical tunneling (QMT) chemistry involving atoms heavier than hydrogen was considered unreasonable. Contributing to the shift of this paradigm, we present here the discovery of a new and distinct heavy-atom QMT reaction. Triplet syn-2-formyl-3-fluorophenylnitrene, generated in argon matrices by UV-irradiation of an azide precursor, was found to spontaneously cyclize to singlet 4-fluoro-2,1-benzisoxazole. Monitoring the transformation by IR spectroscopy, temperature-independent rate constants (k≈1.4×10-3  s-1 ; half-life of ≈8 min) were measured from 10 to 20 K. Computational estimated rate constants are in fair agreement with experimental values, providing evidence for a mechanism involving heavy-atom QMT through crossing triplet to singlet potential energy surfaces. Moreover, the heavy-atom QMT takes place with considerable displacement of the oxygen atom, which establishes a new limit for the heavier atom involved in a QMT reaction in cryogenic matrices.pt
dc.language.isoengpt
dc.publisherWileypt
dc.relationinfo:eu-repo/grantAgreement/POCI-01-0145-FEDER-028973/PTpt
dc.relationinfo:eu-repo/grantAgreement/FCT/UIDP/00313/2020pt
dc.relationinfo:eu-repo/grantAgreement/FCT/00313/2019/PTpt
dc.relationinfo:eu-repo/grantAgreement/FCT/UIP/00313/2020pt
dc.rightsembargoedAccesspt
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/pt
dc.subjectIR spectroscopypt
dc.subjectHeavy-atom tunnelingpt
dc.subjectMatrix isolationpt
dc.subjectNitrenespt
dc.subjectNon-adiabatic transition state theorypt
dc.titleHeavy-Atom Tunneling Through Crossing Potential Energy Surfaces: Cyclization of a Triplet 2-Formylarylnitrene to a Singlet 2,1-Benzisoxazolept
dc.typearticle-
degois.publication.issue40pt
degois.publication.titleAngewandte Chemie (International ed. in English)pt
dc.relation.publisherversionhttps://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202006640pt
dc.peerreviewedyespt
dc.identifier.doi10.1002/anie.202006640pt
degois.publication.volume59pt
dc.date.embargo2021-06-17*
uc.date.periodoEmbargo365pt
item.grantfulltextembargo_20210617-
item.languageiso639-1en-
item.fulltextCom Texto completo-
crisitem.author.deptFaculty of Sciences and Technology-
crisitem.author.deptFaculty of Sciences and Technology-
crisitem.author.parentdeptUniversity of Coimbra-
crisitem.author.parentdeptUniversity of Coimbra-
crisitem.author.researchunitCQC - Coimbra Chemistry Centre-
crisitem.author.researchunitCQC - Coimbra Chemistry Centre-
crisitem.author.parentresearchunitFaculty of Sciences and Technology-
crisitem.author.parentresearchunitFaculty of Sciences and Technology-
crisitem.author.orcid0000-0002-8511-1230-
crisitem.author.orcid0000-0002-8264-6854-
Appears in Collections:I&D CQC - Artigos em Revistas Internacionais
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