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A New Tripodal Ligand System with Steric and Electronic Modularity for Uranium Coordination Chemistry

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journal contribution
posted on 2009-10-05, 00:00 authored by Suzanne C. Bart, Frank W. Heinemann, Christian Anthon, Christina Hauser, Karsten Meyer
The synthesis of a potentially redox active tripodal ligand containing a tris(aryloxide) functionalized mesitylene anchor, ((tBuArOH)3mes) (1), and its metalation with low-valent uranium to form [((tBuArO)3mes)U] (1-U) is reported. The results from characterization by X-ray crystallography, spectroscopic studies, and computational analysis, as well as initial reactivity studies, support a +3 uranium oxidation state. Comparison to the previously synthesized complex, [((tBuArO)3tacn)U] (2-U), featuring the redox-innocent triazacyclononane anchor reveals that changing the anchor from the flexible triazacyclononane to a rigid mesityl fragment increases the structural flexibility of the aryloxide substituents in complexes of 1. The synthesis and crystal structures of uranium(IV) amide complexes of 1-U and 2-U are discussed.