Two polynuclear Th(IV) molecular clusters, one of which co-crystallizes with a novel Th(IV) monomer, were synthesized under ambient conditions from reactions of thorium nitrate with sodium salicylate. The structures of Th6(OH)4O4(C7H5O3)12(DMF)6 (1 ), and Th6O3(OH)5(C7H5O3)12(DMF)6�Th(NO3)5(DMF)2 (2 ) each consist of a core of six Th(IV) cations arranged at the vertices of an octahedron that are bridged via �3-oxo and �3-hydroxo. Th(IV) cations found in the cluster are further coordinated by four bridging carboxylate groups and capped by an oxygen from N,N'-dimethylformamide, resulting in monocapped square antiprismatic geometries. The bridging �3-oxo:�3-hydroxo ratio within the cluster cores differs: in the case of (1 ) it is 4:4, resulting in a net neutral cluster, whereas for (2 ), this ratio is 3:5, resulting in a rare example of a cationic cluster that co-crystallizes with an anionic Th(IV) monomer. The monomeric Th(IV) is a 12-coordinate system that closely resembles the geometry found in U6+ , with two shorter axial bonds to two N,N'-dimethylformamides and ten longer equatorial bonds to nitrate ligands.

Synthesis and characterization of Th(IV) hexanuclear clusters in non-aqueous systems: Co-formation of a novel Th(IV) monomer with an unusual 12-coordinate symmetry

248th National Meeting (2014)

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