Direct Syntheses and Structural Novelty of Lanthanoid Aryloxides with Flexible Radial Arms

Direct treatment of excess lanthanum, europium or ytterbium metal with 2,6‐dibenzylphenol (HOdbp) at 150 °C afforded [La 2 (Odbp) 6 ], [Eu 2 (Odbp) 4 ] and [Yb(Odbp) 2 ] n , respectively, in high yields. Alternatively, treatment of Yb metal with excess HOdbp gave an ytterbium( III ) species [Yb 2 (Odbp) 6 ], similar to the lanthanum analogue. X‐ray crystal structures were obtained for [La 2 (Odbp) 6 ], [Eu 2 (Odbp) 4 ] and [Yb 2 (Odbp) 6 ]. [La 2 (Odbp) 6 ] and [Yb 2 (Odbp) 6 ] are pseudo‐centrosymmetric dimers with two terminal and four bridging Odbp – ligands and [Eu 2 (Odbp) 4 ] crystallizes as a centrosymmetric dimer with further organization in a polymeric form through supramolecular interactions. All three structurally characterized compounds achieve coordination saturation by Ln–π‐arene interactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)