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

被引:82
作者
Bart, Suzanne C. [1 ]
Heinemann, Frank W. [1 ]
Anthon, Christian [1 ]
Hauser, Christina [1 ]
Meyer, Karsten [1 ]
机构
[1] Univ Erlangen Nurnberg, Dept Chem & Pharm, D-91058 Erlangen, Germany
关键词
BIS(IMINO)PYRIDINE IRON; REDUCTIVE REACTIVITY; MOLECULAR-STRUCTURE; HYDRIDE COMPLEXES; CRYSTAL-STRUCTURE; CARBON-MONOXIDE; METAL-COMPLEXES; APPROXIMATION; ACTIVATION; ENERGY;
D O I
10.1021/ic9012697
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
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.
引用
收藏
页码:9419 / 9426
页数:8
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