reaction of lutetium metal with 1.5 equiv of elemental iodine in 2-propanol leads to the isolation of Lul(3)((HOPr)-Pr-i)(4) (1). An X-ray crystal structure reveals an ionic structure with well-separated [Lul(2)((HOPr)-Pr-i)(4)] cations and [I] anions. Dissolution of 1 in pyridine generates the unusual alkoxide species [Lul((OPr)-Pr-i)(py)(5)][I] (2) with the elimination of HI. An X-ray crystal structure of 2 confirmed the ionic nature of the compound, with the cationic portion of the complex exhibiting a seven-coordinated lutetium center with trans-disposed iodo and alkoxide ligands and five pyridine molecules equally displaced within the equatorial plane. Exposure of 2 to iodotrimethylsilane yields the expected triiodide species [Lul(2)(py)(5)][I] (3), which may also be prepared by refluxing commercially available Lul(3) in THF, followed by crystallization from a THF/pyridine mixture. The solid-state structure of 3 is similar to that of 2, with the alkoxide ligand having been replaced by an iodide. The formation of ionic structures 1-3 as opposed to the higher-coordinated neutral species may be traced to the small lutetium center and the presence of relatively strong Lewis bases within the coordination sphere of the metal.