Tuning the locus of oxidation in Cu-diamido-diphenoxo complexes: From Cu(III) to Cu(II)-phenoxyl radical - Université de Lille Accéder directement au contenu
Article Dans Une Revue Inorganica Chimica Acta Année : 2018

Tuning the locus of oxidation in Cu-diamido-diphenoxo complexes: From Cu(III) to Cu(II)-phenoxyl radical

Résumé

While N2O2 tetraanionic ligands containing a strong N-amidate σ-donor are generally assumed to stabilise metal high valence states, we herein have shown that, in dianionic Cu(II)-diamido-diphenoxo complexes, H-bonding and electronic effects on the phenolate groups may modulate the electronic structure of their oxidised species from Cu(III) to Cu(II)-phenoxyl radical complexes; and so in the negative potential range. We observe that electron-poor phenolate complexes 22− and 32− oxidise to Cu(III) species, whereas electron rich phenolate complex 12− oxidises to a Cu(II)-phenoxyl radical. Our DFT results suggest that π-electron-rich phenolate rings in 12− are responsible for an increase of the HOMO orbital energy, bringing the HOMO-SOMO gap small enough to favour a ligand-based oxidation process. Further DFT-calculations have also shown that upon changing the o,p-phenol substituent from electron-widthdrawing groups (NO2) to electron-donating ones (OMe), the favoured oxidised state switches from Cu(III) to Cu(II)-radical. These results emphasize the use of the versatile diamido-diphenoxo backbone as a promising way to novel GO-chemical models, as well as molecular switches.
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Dates et versions

hal-04456758 , version 1 (14-02-2024)

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Meital Eckshtain-Levi, Ronit Lavi, Himanshu Arora, Maylis Orio, Laurent Benisvy. Tuning the locus of oxidation in Cu-diamido-diphenoxo complexes: From Cu(III) to Cu(II)-phenoxyl radical. Inorganica Chimica Acta, 2018, Inorganica Chimica Acta, 481, pp.143-150. ⟨10.1016/j.ica.2017.09.049⟩. ⟨hal-04456758⟩
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