Ytterbium metal reacts with iodine to generate ytterbium diiodide directly, which can react with diselenides to form ytterbium selenolates (RSeYbI 2). These species reacted smoothly with allyl bromide to give allylselenides in moderate to good yields under neutral conditions. Ytterbium metal reacts with iodine to generate ytterbium diiodide directly, which can react with diselenides to form ytterbium selenolates (RSeYbI 2). These species reacted smoothly with allyl bromide to give allylselenides in moderate to good yields under neutral conditions.