Synthesis and reactivity of uranium(IV) amide complexes supported by a triamidotriazacyclononane ligand.
Synthesis and reactivity of uranium(IV) amide complexes supported by a triamidotriazacyclononane ligand.
复制标题
三酰胺三氮杂环壬烷配体支持的铀（IV）酰胺配合物的合成和反应性。
作者：
M. A. Antunes;M. Dias;B. Monteiro;A. Domingos;I. Santos;N. Marques
[U{（SiMe_2NPh）_3-tacn}Cl]与LiNEt_2或LiNPh_2反应得到相应的酰胺化合物[U{（SiMe_2NPh）_3-tacn}（NR_2）]（R = Et（1），R = Ph（2））。配合物已充分其特征在于通过光谱方法和1的固态结构由单晶X-射线衍射分析确定。三（二甲基甲硅烷基苯胺）三氮杂环壬烷配体的六个氮原子呈三棱柱构型，其中二乙基酰胺配体的氮原子封端三棱柱的三角面之一。2从CH_3CN溶液中结晶得到六元杂环[U{（SiMe_2NPh）_3-tacn}{κ_2-（HNC（Me））_2CC[三键]N}]（3）的晶体。研究了酰胺的反应活性。这两种化合物与质子底物HOC 6 H2 - 2，4，6-Me 3，3，5-Me 2 pzH（pz =吡唑基）和HSC 5 H4 N发生酸碱反应，得到相应的[U{（SiMe 2NPh）3-tacn}X]（X = OC 6 H2 - 2，4，6-Me 3（4），3，5-Me 2 pzH（5），kappa 2-SC 5 H4 N（6））配合物。通过单晶X射线衍射测定了化合物和的固态结构，结果表明化合物均为八配位十二面体构型。
Reaction of [U{(SiMe2NPh)3-tacn}Cl] with LiNEt2 or LiNPh2 affords the corresponding amide compounds, [U{(SiMe2NPh)3-tacn}(NR2)] (R = Et (1), R = Ph (2)). The complexes have been fully characterized by spectroscopic methods and the solid-state structure of 1 was determined by single-crystal X-ray diffraction analysis. The six nitrogen atoms of the tris(dimethylsilylanilide)triazacyclononane ligand are in a trigonal prismatic configuration with the nitrogen atom of the diethylamide ligand capping one of the trigonal faces of the trigonal prism. Crystallization of 2 from CH3CN solution gave crystals of the six-membered heterocycle [U{(SiMe2NPh)3-tacn}{kappa2-(HNC(Me))2CC[triple bond]N}] (3). The reactivity of the amides was investigated. Both compounds undergo acid-base reactions with protic substrates such as HOC6H2-2,4,6-Me3, 3,5-Me2pzH (pz = pyrazolyl) and HSC5H4N to give the corresponding [U{(SiMe2NPh)3-tacn}X] (X = OC6H2-2,4,6-Me3 (4), 3,5-Me2pzH (5), kappa2-SC5H4N (6)) complexes. The solid-state structures of and were determined by single-crystal X-ray diffraction and revealed that the compounds are eight-coordinate with dodecahedral geometry.
影响因子：
4.9
作者：
Castro-Rodriguez, I;Olsen, K;Meyer, K
通讯作者：
Meyer, K
影响因子：
15
作者：
Castro-Rodriguez, I;Olsen, K;Meyer, K
通讯作者：
Meyer, K