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

作者:Bart Suzanne C; Heinemann Frank W; Anthon Christian; Hauser Christina; Meyer Karsten*
来源:Inorganic Chemistry, 2009, 48(19): 9419-9426.
DOI:10.1021/ic9012697

摘要

The synthesis of a potentially redox active tripodal ligand containing a tris(aryloxide) functionalized mesitylene anchor, (((ArOH)-Ar-tBu)(3)mes) (1), and its metalation with low-valent uranium to form [(((ArO)-Ar-tBu)(3)mes)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, [(((ArO)-Ar-tBu)(3)tacn)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.

  • 出版日期2009-10-5