Synthesis and Characterization of Pyridine Dipyrrolide Uranyl Complexes.

ABSTRACT: The first actinide complexes of the pyridine dipyrrolide (PDP) ligand class, (^MesPDP^Ph)UO₂(THF) and (^Cl2PhPDP^Ph)UO₂(THF), are reported as the U^VI uranyl adducts of the bulky aryl substituted pincers (^MesPDP^Ph)^2- and (^Cl2PhPDP^Ph)^2- (derived from 2,6-bis(5-(2,4,6-trimethylphenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine (H₂^MesPDP^Ph, Mes = 2,4,6-trimethylphenyl), and 2,6-bis(5-(2,6-dichlorophenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine (H₂^Cl2PhPDP^Ph, Cl₂Ph = 2,6-dichlorophenyl), respectively). Following the in situ deprotonation of the proligand with lithium hexamethyldisilazide to generate the corresponding dilithium salts (e.g., Li₂^ArPDP^Ph, Ar = Mes of Cl₂Ph), salt metathesis with [UO₂Cl₂(THF)₂]₂ afforded both compounds in moderate yields. The characterization of each species has been undertaken by a combination of solid- and solution-state methods, including combustion analysis, infrared, electronic absorption, and NMR spectroscopies. In both complexes, single-crystal X-ray diffraction has revealed a distorted octahedral geometry in the solid state, enforced by the bite angle of the rigid meridional (^ArPDP^Ph)^2- pincer ligand. The electrochemical analysis of both compounds by cyclic voltammetry in tetrahydrofuran (THF) reveals rich redox profiles, including events assigned as U^VI/U^V redox couples. A time-dependent density functional theory study has been performed on (^MesPDP^Ph)UO₂(THF) and provides insight into the nature of the transitions that comprise its electronic absorption spectrum.

SUBMITTER: Hakey BM 

PROVIDER: S-EPMC9044449 | biostudies-literature | 2022 Apr

REPOSITORIES: biostudies-literature