Synthesis and Characterization of Thorium(IV) and Uranium(IV) Corrole Complexes

By Ward, Ashleigh L.; Buckley, Heather L.; Lukens, Wayne W. & Arnold, John
Published in Journal of the American Chemical Society NULL 2013

Abstract

The first examples of actinide complexes incorporating corrole ligands are presented. Thorium(IV) and uranium(IV) macrocycles of Mes2(p-OMePh)corrole were synthesized via salt metathesis with the corresponding lithium corrole in remarkably high yields (93% and 83%, respectively). Characterization by single-crystal X-ray diffraction revealed both complexes to be dimeric, having two metal centers bridged via bis(μ-chlorido) linkages. In each case, the corrole ring showed a large distortion from planarity, with the Th(IV) and U(IV) ions residing unusually far (1.403 and 1.330 Å, respectively) from the N4 plane of the ligand. 1H NMR spectroscopy of both the Th and U dimers revealed dynamic solution behavior. In the case of the diamagnetic thorium corrole, variable-temperature, DOSY (diffusion-ordered) and EXSY (exhange) 1H NMR spectroscopy was employed and supported that this behavior was due to an intrinsic pseudorotational mode of the corrole ring about the M -M axis. Additionally, the electronic structure of the actinide corroles was assessed using UV -vis spectroscopy, cyclic voltammetry, and variable-temperature magnetic susceptibility. This novel class of macrocyclic complexes provides a rich platform in an underdeveloped area for the study of nonaqueous actinide bonding and reactivity.

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