Reaction of 3 equiv of 2,6-diisopropylphenol with Ln[N(SiMe3)2]3 (Ln = Nd, Sm, Er) in refluxing toluene and subsequent crystallization yield pale blue (Nd), deep yellow (Sm), or light pink (Er) crystals of the tris(aryloxide) complexes Ln2(O-2,6-i-Pr2C6H3)6 (Ln = Nd (1), Sm (2), Er (3)) in good yield. X-ray crystallographic studies of 1 and 2 reveal centrosymmetric, dimeric units bridged by eta6-pi-arene interactions of a unique aryloxide ligand. Ln-O bond lengths average 2.122(9) (1, Nd) and 2.101(6) angstrom (2, Sm) for terminal ligands and 2.211(8) (1) and 2.198(5) angstrom (2) for bridging aryloxide ligands. Eta6-Arene bridges hold the dimeric units together with an average Ln-C distance of 3.035 angstrom for 1 and 2.986 and 3.016 angstrom for the two independent molecules in the asymmetric unit of 2. Compounds 1-3 react with THF in toluene solution to give the THF bisadducts Ln(O-2,6-i-Pr2C6H3)3(THF)2 (Ln = Nd (4), Sm (5), Er (6)) in essentially quantitative yield. In a related fashion, Lu(O-2,6-i-Pr2C6H3)3(THF)2 (7) was prepared following the reaction of Lu[N(SiMe3)2]3 with 3 equiv of diisopropylphenol in the presence of THF. The anhydrous trichlorides of Sm, Pr, Gd, and Yb react with 3 equiv of potassium 2,6-diisopropylphenoxide in THF solution to give the 5-coordinate THF bisadducts Ln(O-2,6-i-Pr2C6H3)3(THF)2 (Ln = Sm (5), Pr (8), Gd (9), Yb (10)). X-ray crystal structures have been obtained for Ln(O-2,6-i-Pr2C6H3)3(THF)2 (Ln = Er (6), Lu (7), Pr (8), Gd(9)), The four compounds are isostructural, and the molecular structure consists of a distorted trigonal bipyramidal lanthanide metal center with two axial THF and three equatorial aryloxide ligands. Ln-O distances for the aryloxide ligands average 2.078 (6, Er), 2.044 (7, Lu), 2.172 (8, Pr), and 2.130 (9, Gd) while Ln-O distances for the THF ligands average 2.346 (6), 2.296 (7), 2.482 (8), and 2.394 angstrom (9).