LAUSR

The σ-donor ligand selone L (L = 1,3-dibutylbenzimidazolin-2-selone, C15H22N2Se) caused cleavage of the Te–Te bond of the mixed-valent phenyltellurenyl bromide {Ph(Br2)TeTePh} in THF to produce the selone adduct of a phenyltellurenyl cation with phenyltellurium dibromide anion, [PhTe(L)][PhTeBr2] (1). The adduct disproportionated in polar solvent (CH3CN), followed by hydrolysis with traces of water to give the largest telluroxane cluster, [{(C6H5)Te}19O24Br5]Br4, with a Te19O24 skeleton. The bowl-shaped telluroxane cluster dimerizes in the solid state, forming the molecular capsule {[{(C6H5)Te}19O24Br5]Br4}2. The cluster is amphipathic and has a hydrophilic cavity consisting of tellurium, oxygen, and bromide atoms, which contains 24H2O molecules.