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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. This is shown in the fixed ligand arrangement of pyren and salen in the respective An^IV complexes. The overall bond strength of the pure N-donor ligand pyren to An^IV (An=Th, U, Np, Pu) is slightly weaker than to salen, with the exception of the Pa^IV complex, which exhibits extraordinarily high electron sharing of pyren with Pa^IV . Such an altered ligand preference within the early An^IV series points to a specificity of the 5f¹ configuration, which can be explained by polarisation effects of the 5 f electrons, allowing the strongest f electron backbonding from Pa^IV (5f¹ ) to the N donors of pyren.

SUBMITTER: Kohler L

PROVIDER: S-EPMC9299701 | biostudies-literature |

REPOSITORIES: biostudies-literature

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