Uncommon assembling of organotellurium iodides: Synthesis and X-ray characterization of [mesTeI(μ-I)2(TeImes)2]n, (C5H6N)4[mesTeI2]2(I3)2 and {(C5H6N)3[(mesTeI3)(μ-I−)(TeI3mes)](I3)2}n (mes = 2,4,6-trimethylphenyl)

(MesTe)2 (mes = 2,4,6-trimethylphenyl) reacts with iodine in the presence of KI to give [mesTeI(μ-I)2(TeImes)2]n (1). If pyridinium iodide and two or five equivalents of I2 are added to the mixture (mesTe)2/iodine, then (C5H6N)4 [mesTeI2]2(I3)2 (2) and {(C5H6N)3[(mesTeI3) (μ-I−)(TeI3mes)](I3)2}n (3) are produced in good yields. Compounds 1, 2 and 3 are atypical structured organotellurium iodides, attaining interionic I3-⋯I–Te-, N+–H⋯I–Te− and N+–H⋯I3- secondary interactions. Complex 2 form single dimers, 1 and 3 assemble onedimensional, polymeric chains. In the neutral compound 1 tellurium occurs in the oxidation states +2 and +4. Besides the occurrence of charge transfer (CT) systems associated to the I3- ions, the charge delocalization in compound 3 suggests further the existence of an inner CT system within the iodine atoms I(3), I(4) and I(5).

Graphical abstract(MesTe)2 (mes = mesityl) reacts with I2 in the presence of KI to give [mesTeI(μ-sI)2(TeImes)2]n (1). If (PyH)I and two/five equivalents of I2 are added to the mixture (mesTe)2/iodine, (C5H6N)4[mesTeI2]2(I3)2 (2) and {(C5H6N)3[(mesTeI3)(μ-I−)(TeI3mes)](I3)2}n (3) are produced. Complex 2 form single dimers, 1 and 3 assemble polymeric chains. In compound 1 tellurium occurs as TeII and TeIV. Charge Transfer (CT) systems are associated to the I3- ions and 3 probably encloses also an inner CT system.Figure optionsDownload full-size imageDownload as PowerPoint slide