The complexes named in the title (η5-C9H7)3Ln·OC4H8 (Ln Nd, Gd, Er) were synthesized by the reaction of anhydrous lanthanide trichlorides with indenyl potassium and cyclooctadienyl potassium (1:2:1 molar ratio) in THF. The complexes were characterized by elemental analysis, infrared and 1H-NMR spectroscopy, and mass spectrometry. In addition, the crystal structures of (η5-C9H7)3Nd·OC4H8 (1) and (η5-C9H7)3Gd·OC4H8 (2) were determined by an X-ray diffraction study. Complexes 1 and 2 belong to hexagonal space group P63 with unit cell parameters a = b = 11.843(3), c = 10.304(4) Å, V = 1251.7(9) Å3, Dc = 1.49 g·cm−, Z = 2 for 1, and a = b = 11.805(2), c = 10.236(2) Å, V = 1235.4(6) Å3, Dc = 1.54 g·−3, Z = 2 for 2. The structures were solved by Patterson and Fourier techniques and refined by least-squared to final discrepancy indices of R = 0.049, Rw = 0.053 using 925 independent reflections with I ⩾ 3σ(I for 1, and R = 0.23, Rw = 0.025 using 1327 independent reflections with I ⩾ 3σ(I) for 2. Coordination numbers for Nd3+ and Gd3+ are 10; the average bond lengths NdO and GdO are 2.557(21) and 2.459(13) Å, respectively. The structural studies showed the complexes to have 3-fold symmetry, but the THF molecule has no such symmetry; consequently the arrangement of carbon atoms in the THF molecule are disordered.
Anhydrous lanthanide trichlorides react with phenyl lithium in THF(tetrahydrofuran) to give the complexes, C6H5LnCl2·nTHF (Ln = Pr, Sm, Gd; n = 3, 4). The crystal structure of the C6H5GdCl2·4THF was determined by X-ray diffraction, orthorhombic space group Ccm21, a 12.776(6), b 12.954(6), c 15.802(3) Å, V 2615.4(1.8) Å3, Z = 4. The final R is 0.0438, Rw 0.0445, Gd3+ coordination number 7. The length of the GdC bond is 2.416(24) Å, the average GdCl bond length is 2.677(8) Å, that of GdO is 2.508(4) Å, and the CC distance in the phenyl group is 1.378(41) Å.
