RT journal article
T1 Characterization of a Ferryl Flip in Electronically Tuned Nonheme Complexes. Consequences in Hydrogen Atom Transfer Reactivity
A1 Dantignana, Valeria
A1 Pérez Segura, María del Carmen
A1 Besalú Sala, Pau
A1 Delgado Pinar, Estefanía
A1 Martínez Camarena, Álvaro
A1 Serrano Plana, Joan
A1 Álvarez Núñez, Andrea
A1 Castillo González, Carmen Esther
A1 García España, Enrique
A1 Luis, Josep M.
A1 García Basallote, Manuel
A1 Costas, Miquel
A2 Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica
K1 Atom Transfer
K1 Iron
K1 Isomerization
K1 Oxidation
K1 Oxoiron
AB 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.
PB Wiley
SN 1433-7851
YR 2022
FD 2022-10-28
LK http://hdl.handle.net/10498/29360
UL http://hdl.handle.net/10498/29360
LA eng
DS Repositorio Institucional de la Universidad de Cádiz
RD 21-sep-2026