How 5 f Electron Polarisability Drives Covalency and Selectivity in Actinide N-Donor Complexes.

ABSTRACT: We report a series of isostructural tetravalent actinide (Th, U-Pu) complexes with the N-donor ligand N,N'-ethylene-bis((pyrrole-2-yl)methanimine) (H₂ L, H₂ pyren). Structural data from SC-XRD analysis reveal [An(pyren)₂ ] complexes with different An-N_imine versus An-N_pyrrolide bond lengths. Quantum chemical calculations elucidated the bonding situation, including differences in the covalent character of the coordinative bonds. A comparison to the intensely studied analogous N,N'-ethylene-bis(salicylideneimine) (H₂ salen)-based complexes [An(salen)₂ ] displays, on average, almost equal electron sharing of pyren or salen with the An^IV , pointing to a potential ligand-cage-driven complex stabilisation. Th

SUBMITTER: Kohler L 

PROVIDER: S-EPMC9299701 | biostudies-literature | 2021 Dec

REPOSITORIES: biostudies-literature