Role of the Meso Substituent in Defining the Reduction of Uranyl Dipyrrin Complexes - Archive ouverte HAL
Article Dans Une Revue Inorganic Chemistry Année : 2022

Role of the Meso Substituent in Defining the Reduction of Uranyl Dipyrrin Complexes

Résumé

The uranyl complex U$^{VI}$O$_2$Cl(L$^{Mes}$) of the redox-active, acyclic dipyrrin–diimine anion L$^{Mes}$– [HL$^{Mes}$ = 1,9-di-tert-butyl-imine-5-(mesityl)dipyrrin] is reported, and its redox property is explored and compared with that of the previously reported U$^{VI}$O$_2$Cl(LF) [HLF = 1,9-di-tert-butyl-imine-5-(pentafluorophenyl)dipyrrin] to understand the influence of the meso substituent. Cyclic voltammetry, electron paramagnetic resonance spectroscopy, and density functional theory studies show that the alteration from an electron-withdrawing meso substituent to an electron-donating meso substituent on the dipyrrin ligand significantly modifies the stability of the products formed after reduction. For UVIO2Cl(LMes), the formation of a diamond-shaped, oxo-bridged uranyl(V) dimer, [U$^V$O$_2$(L$^{Mes}$)]$_2$ is seen, whereas in contrast, for UVIO2Cl(LF), only ligand reduction occurs. Computational modeling of these reactions shows that while ligand reduction followed by chloride dissociation occurs in both cases, ligand-to-metal electron transfer is favorable for U$^{VI}$O$_2$Cl(L$^{Mes}$) only, which subsequently facilitates uranyl(V) dimerization.
Fichier principal
Vignette du fichier
287866.pdf (4.16 Mo) Télécharger le fichier
Origine Publication financée par une institution

Dates et versions

hal-04116999 , version 1 (24-09-2024)

Identifiants

Citer

Karlotta van Rees, Thayalan Rajeshkumar, Laurent Maron, Stephen Sproules, Jason Love. Role of the Meso Substituent in Defining the Reduction of Uranyl Dipyrrin Complexes. Inorganic Chemistry, 2022, 61 (50), pp.20424-20432. ⟨10.1021/acs.inorgchem.2c03048⟩. ⟨hal-04116999⟩
19 Consultations
0 Téléchargements

Altmetric

Partager

More