| Abstract |
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[(SiMe2NPh)(3)-tacn](THF)(2)) gives good yields of the compounds [M\(SiMe2NPh)(3)-tacn\] (M = Y (1), Eu (3), Yb (4)) and [La\(SiMe2NPh)(3)-tacn\(THF)] (2). Reduction of 3 with Na/Hg followed by recrystallization in the presence of diglyme yielded crystals of [Eu\(SiMe2NPh)(3)-tacn\][Na-(diglyme)(2)] (5). Synthesis of the uranium(III) complex [U\(SiMe2NPh)(3)-tacn\] (6) is achieved by reaction of 1 equiv of Na-3[(SiMe2NPh)(3)-tacn](THF)(2) with uranium triiodide. The U(IV) complexes, [U\(SiMe2NPh)(3)-tacn\X] (X = Cl (7); I (8)), were prepared via oxidation of 6 with benzyl chloride or I-2, but salt metathesis from UCl4 provided a higher yield route for 7. The solid-state structures of 1-7 were determined by single-crystal X-ray diffraction. The ligand [(SiMe2NPh)(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. |
