Large Telluroxane Bowls Connected by a Layer of Iodine Ions

Phenyltelluroxane clusters of the composition [{(PhTe)(19)O(24)}(2)I(18)(solv)] (1) are formed during the hydrolysis of [PhTeI(3)](2) or the oxidation of various phenyltellurium(II) compounds with iodine under hydrolytic conditions. The compounds consist of two half‐spheres with a {(PhTe)(19)O(24)}(9+) network, which are connected by 18 iodine atoms. The spherical clusters can accommodate solvent molecules such as pyridine or methanol in the center of two rings formed by iodine atoms. The presence of other metal ions during the cluster formation results in a selective replacement of the central {PhTe}(3+) units of each half‐sphere as has been demonstrated with the isolation of [{(PhTe)(18)({Ca(H(2)O)(2)}O(24)}(2)I(16)] (2) and [{(PhTe)(18)({Y(NO(3))(H(2)O)}O(24)}(2)I(16)] (3). A crownether‐like coordination by six oxygen atoms of the telluroxane network is found for the {Ca(H(2)O}(2)}(2+) and {Y(NO(3))(H(2)O)}(2+) building blocks. Mass spectrometric studies show that considerable amounts of the intact clusters are transferred to the gas phase without dissociation.