Triamidotriazacyclononane complexes of group 3 metals. Synthesis and crystal structures.
Triamidotriazacyclononane complexes of group 3 metals. Synthesis and crystal structures.
复制标题
第 3 族金属的三酰胺三氮杂环壬烷配合物。
作者：
B. Monteiro;D. Roitershtein;Humberto S. Ferreira;J. Ascenso;Ana M. Martins;A. Domingos;N. Marques
钇与三氯化镧的反应（Ln = La，Eu，Yb）与1当量的1，4，7-三（1，4，（二甲基硅基苯胺）-1，4，7-三氮杂环壬烷（Na（3）[（SiMe（2）NPh）（3）-tacn]（THF）（2））得到了较好的化合物[M[（SiMe（2）NPh）（3）-tacn]]的产率（M = Y（1），Eu（3），Yb（4））和[La[（SiMe（2）NPh）（3）-tacn]（THF）]（2）。用Na/Hg还原3，然后在二甘醇二甲醚存在下重结晶，得到[Eu[（SiMe（2）NPh）（3）-tacn]][Na（diglyme）（2）]（5）晶体。铀（III）配合物[U[（SiMe（2）NPh）（3）-tacn]]（6）的合成是通过1当量的Na（3）[（SiMe（2）NPh）（3）-tacn]（THF）（2）与三碘化铀反应来实现的。U（IV）配合物[U[（SiMe（2）NPh）（3）-tacn]X]（X = Cl（7）; I（8））是通过用苄基氯或I（2）氧化6制备的，但UCl（4）的盐复分解提供了7的更高产率途径。通过单晶X射线衍射测定了1-7的固态结构。配体[（SiMe（2）NPh）（3）-tacn]为中性配合物1、3、4和6中的金属中心以及离子配合物5中的金属中心产生三角棱柱配位环境。在2中，配体的六个氮原子处于三棱柱构型，THF的氧原子覆盖三棱柱的三角形面之一。在7中，铀原子周围的配位几何形状最好描述为双帽三角双锥。
Reaction of yttrium and lanthanide trichlorides (Ln = La, Eu, Yb) with 1 equiv of the trisodium salt of 1,4,7-tris(dimethylsilylaniline)-1,4,7-triazacyclononane (Na(3)[(SiMe(2)NPh)(3)-tacn](THF)(2)) gives good yields of the compounds [M[(SiMe(2)NPh)(3)-tacn]] (M = Y (1), Eu (3), Yb (4)) and [La[(SiMe(2)NPh)(3)-tacn](THF)] (2). Reduction of 3 with Na/Hg followed by recrystallization in the presence of diglyme yielded crystals of [Eu[(SiMe(2)NPh)(3)-tacn]][Na(diglyme)(2)] (5). Synthesis of the uranium(III) complex [U[(SiMe(2)NPh)(3)-tacn]] (6) is achieved by reaction of 1 equiv of Na(3)[(SiMe(2)NPh)(3)-tacn](THF)(2) with uranium triiodide. The U(IV) complexes, [U[(SiMe(2)NPh)(3)-tacn]X] (X = Cl (7); I (8)), were prepared via oxidation of 6 with benzyl chloride or I(2), but salt metathesis from UCl(4) provided a higher yield route for 7. The solid-state structures of 1-7 were determined by single-crystal X-ray diffraction. The ligand [(SiMe(2)NPh)(3)-tacn] generates a trigonal prismatic coordination environment for the metal center in the neutral complexes 1, 3, 4, and 6 and the ionic 5. In 2 the six nitrogen atoms of the ligand are in a trigonal prismatic configuration with the oxygen atom of the THF capping one of the triangular faces of the trigonal prism. In 7 the coordination geometry around the uranium atom is best described as bicapped trigonal bipyramidal.