Lanthanoiden-komplexe: VI. Monomere homoleptische Ln(RDoCP) 3-komplexe (Ln La, Nd) mit aminofunktionalisierten cyclopentadienyl-Liganden
1993
Abstract The complexes Ln(Me 2 NC 2 H 4 CP) 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 2 NC 2 H 4 CP) 2 Cl ( 4 ). These complexes sublime below 175°C/10 −3 mm Hg. Single-crystal X-Ray structures performed for 2 and 3 reveal mono nuclear 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, R w = 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, R w = 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) A), the larger lanthanum(III) centre of 3 is approached by a further nitrogen donor group (La-N2 2.898(6) A, La-N1 3.688(5) A).
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