Characterization of a Ferryl Flip in Electronically Tuned Nonheme Complexes. Consequences in Hydrogen Atom Transfer Reactivity
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. Int…
Understanding light-driven H2 evolution through the electronic tuning of aminopyridine cobalt complexes† †Electronic supplementary information (ESI) available. CCDC 1578284–1578289. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04328g
Electronic effects provide a general mechanistic scenario for rationalizing photocatalytic water reduction activity with aminopyridine cobalt complexes.
Understanding light-driven H 2 evolution through the electronic tuning of aminopyridine cobalt complexes
A new family of cobalt complexes with the general formula [CoII(OTf)2(Y,XPyMetacn)] (1R,Y,XPyMetacn ¼ 1-[(4-X-3,5-Y-2-pyridyl)methyl]-4,7-dimethyl-1,4,7-triazacyclononane, (X ¼ CN (1CN), CO2Et (1CO2Et), Cl (1Cl), H(1H), NMe2 (1NMe2)) where (Y ¼ H, and X ¼ OMe when Y ¼ Me (1DMM)) is reported. We found that the electronic tuning of the Y,XPyMetacn ligand not only has an impact on the electronic and structural properties of the metal center, but also allows for a systematic water-reduction-catalytic control. In particular, the increase of the electron-withdrawing character of the pyridine moiety promotes a 20-fold enhancement of the catalytic outcome. By UV-Vis spectroscopy, luminescence quenc…
CCDC 1578287: Experimental Crystal Structure Determination
Related Article: Arnau Call, Federico Franco, Noufal Kandoth, Sergio Fernández, María González-Béjar, Julia Pérez-Prieto, Josep M. Luis, Julio Lloret-Fillol|2018|Chemical Science|9|2609|doi:10.1039/C7SC04328G
CCDC 2192965: Experimental Crystal Structure Determination
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CCDC 2192964: Experimental Crystal Structure Determination
Related Article: 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|2023|Angew.Chem.,Int.Ed.|62||doi:10.1002/anie.202211361
CCDC 1578289: Experimental Crystal Structure Determination
Related Article: Arnau Call, Federico Franco, Noufal Kandoth, Sergio Fernández, María González-Béjar, Julia Pérez-Prieto, Josep M. Luis, Julio Lloret-Fillol|2018|Chemical Science|9|2609|doi:10.1039/C7SC04328G
CCDC 1578286: Experimental Crystal Structure Determination
Related Article: Arnau Call, Federico Franco, Noufal Kandoth, Sergio Fernández, María González-Béjar, Julia Pérez-Prieto, Josep M. Luis, Julio Lloret-Fillol|2018|Chemical Science|9|2609|doi:10.1039/C7SC04328G
CCDC 2192963: Experimental Crystal Structure Determination
Related Article: 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|2023|Angew.Chem.,Int.Ed.|62||doi:10.1002/anie.202211361
CCDC 1578285: Experimental Crystal Structure Determination
Related Article: Arnau Call, Federico Franco, Noufal Kandoth, Sergio Fernández, María González-Béjar, Julia Pérez-Prieto, Josep M. Luis, Julio Lloret-Fillol|2018|Chemical Science|9|2609|doi:10.1039/C7SC04328G
CCDC 2192962: Experimental Crystal Structure Determination
Related Article: 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|2023|Angew.Chem.,Int.Ed.|62||doi:10.1002/anie.202211361
CCDC 1578284: Experimental Crystal Structure Determination
Related Article: Arnau Call, Federico Franco, Noufal Kandoth, Sergio Fernández, María González-Béjar, Julia Pérez-Prieto, Josep M. Luis, Julio Lloret-Fillol|2018|Chemical Science|9|2609|doi:10.1039/C7SC04328G
CCDC 1578288: Experimental Crystal Structure Determination
Related Article: Arnau Call, Federico Franco, Noufal Kandoth, Sergio Fernández, María González-Béjar, Julia Pérez-Prieto, Josep M. Luis, Julio Lloret-Fillol|2018|Chemical Science|9|2609|doi:10.1039/C7SC04328G