Characterization of a Ferryl Flip in Electronically Tuned Nonheme Complexes. Consequences in Hydrogen Atom Transfer Reactivity
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Characterization of a Ferryl Flip in Electronically Tuned Nonheme Complexes. Consequences in Hydrogen Atom Transfer Reactivity

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Characterization of a Ferryl Flip in Electronically Tuned Nonheme Complexes. Consequences in Hydrogen Atom Transfer Reactivity

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dc.contributor.author Dantignana, Valeria
dc.contributor.author Pérez-Segura, M. Carmen
dc.contributor.author Besalú-Sala, Pau
dc.contributor.author Delgado Pinar, Estefanía
dc.contributor.author Martínez Camarena, Álvaro
dc.contributor.author Serrano-Plana, Joan
dc.contributor.author Álvarez-Núñez, Andrea
dc.contributor.author Castillo, Carmen E.
dc.contributor.author Garcia-España Monsonis, Enrique
dc.contributor.author Luis, Josep M.
dc.contributor.author Basallote, Manuel G.
dc.contributor.author Costas, Miquel
dc.contributor.author Company, Anna
dc.date.accessioned 2023-01-24T14:10:52Z
dc.date.available 2023-01-24T14:10:52Z
dc.date.issued 2023
dc.identifier.uri https://hdl.handle.net/10550/85106
dc.description.abstract Two oxoiron(IV) isomers (R2a and R2b) of general formula [FeIV(O)(RPyNMe3)(CH3CN)]2+ are obtained by reaction of their iron(II) precursor with NBu4IO4. The two isomers differ in the position of the oxo ligand, cis and trans to the pyridine donor. The mechanism of isomerization between R2a and R2b has been determined by kinetic and computational analyses uncovering an unprecedented path for interconversion of geometrical oxoiron(IV) isomers. The activity of the two oxoiron(IV) isomers in hydrogen atom transfer (HAT) reactions shows that R2a reacts one order of magnitude faster than R2b, which is explained by a repulsive noncovalent interaction between the ligand and the substrate in R2b. Interestingly, the electronic properties of the R substituent in the ligand pyridine ring do not have a significant effect on reaction rates. Overall, the intrinsic structural aspects of each isomer define their relative HAT reactivity, overcoming changes in electronic properties of the ligand.
dc.language.iso eng
dc.relation.ispartof Angewandte Chemie, 2023, vol. 62, num. 2, p. e202211361
dc.rights.uri info:eu-repo/semantics/openAccess
dc.source Dantignana, Valeria Pérez-Segura, M. Carmen Besalú-Sala, Pau Delgado Pinar, Estefanía Martínez Camarena, Álvaro Serrano-Plana, Joan Álvarez-Núñez, Andrea Castillo, Carmen E. Garcia-España Monsonis, Enrique Luis, Josep M. Basallote, Manuel G. Costas, Miquel Company, Anna 2023 Characterization of a Ferryl Flip in Electronically Tuned Nonheme Complexes. Consequences in Hydrogen Atom Transfer Reactivity Angewandte Chemie 62 2 e202211361
dc.subject Àtoms
dc.subject Reaccions químiques
dc.title Characterization of a Ferryl Flip in Electronically Tuned Nonheme Complexes. Consequences in Hydrogen Atom Transfer Reactivity
dc.type info:eu-repo/semantics/article
dc.date.updated 2023-01-24T14:10:52Z
dc.identifier.doi https://doi.org/10.1002/anie.202211361
dc.identifier.idgrec 156558

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