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

Autor: Valeria Dantignana, M. Carmen Pérez‐Segura, Pau Besalú‐Sala, Estefanía Delgado‐Pinar, Álvaro Martínez‐Camarena, Joan Serrano‐Plana, Andrea Álvarez‐Núñez, Carmen E. Castillo, Enrique García‐España, Josep M. Luis, Manuel G. Basallote, Miquel Costas, Anna Company
Rok vydání: 2022
Předmět:
Zdroj: 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
ISSN: 1521-3757
0044-8249
Popis: 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.
Databáze: OpenAIRE
Externí odkaz: