Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander University of Erlangen-Nuremberg, Egerlandstrasse 1, 91058 Erlangen, Germany.
Inorg Chem. 2009 Oct 5;48(19):9419-26. doi: 10.1021/ic9012697.
The synthesis of a potentially redox active tripodal ligand containing a tris(aryloxide) functionalized mesitylene anchor, (((tBu)ArOH)(3)mes) (1), and its metalation with low-valent uranium to form [(((tBu)ArO)(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, [(((tBu)ArO)(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.
报告了一种可能具有氧化还原活性的三足配体的合成，该配体含有三（芳氧基）功能化均三甲苯锚，（（（tBu）ArOH）（3）mes）（1），并将其与低价铀金属化形成[（（（tBu）ArO）（3）mes）U]（1-U）。通过 X 射线晶体学、光谱研究和计算分析以及初始反应性研究进行的表征结果支持 +3 铀氧化态。与之前合成的配合物[（（（tBu）ArO）（3）tacn）U]（2-U）相比，该配合物具有氧化还原惰性的三氮杂环壬烷锚，结果表明，将配体从柔性三氮杂环壬烷变为刚性均三甲苯片段，增加了配合物 1 中芳氧基取代基的结构灵活性。讨论了铀（IV）酰胺配合物 1-U 和 2-U 的合成和晶体结构。
