Lanthanoiden-komplexe: VI. Monomere homoleptische Ln(R DoCP) 3-komplexe (Ln  La, Nd) mit aminofunktionalisierten cyclopentadienyl-Liganden

Abstract

The complexes Ln(Me 2NC 2H 4CP) 3 [Ln  Nd ( 2), La ( 3)] were synthesized by reaction of LnCl 3 with potassium cyclopentadienide 1 in tetrahydrofuran (THF) at room temperature (1:3 molar ratio), while the same reaction of lutetium(III) chloride yields the complex Lu(Me 2NC 2H 4CP) 2Cl ( 4). These complexes sublime below 175°C/10 −3 mm Hg. Single-crystal X-Ray structures performed for 2 and 3 reveal mononuclear structures. Crystals were obtained by slow evaporation of saturated n-hexane solutions ( 2: space group Pbca, orthorhombic, a = 1294.3(3) pm, b = 1711.8(1) pm, c = 4785.7(6) pm; V = 10603 × 10 6 pm 3; Z = 16; D = 1.385 g cm −1; R = 0.055, Rw = 0.058; 3: space group Cc, monoclinic, a = 1241.3(13), b = 2458.9 (2), c = 859.0(3) β = 98.85(2); V= 2590.6 × 10 6 pm 3; Z = 4; D = 1.404; R = 0.038, Rw = 0.045). Structural details are explained in terms of the metal ionic radii of La III and Nd III, while in 2 the trivalent neodymium is coordinated by three η 5-cyclopentadienyl ligands and the nitrogen atom of one N-donor functionality (Nd-N2 2.73(1), Nd-N6 2.70(1) Å), the larger lanthanum(III) centre of 3 is approached by a further nitrogen donor group (La-N2 2.898(6) Å, La-N1 3.688(5) Å).