X-ray characterization of Te(S2CNC5H10)2 and TeI2[(C13H10N2S)2] · 4C4H8TeI2; the first Te–C bond cleaved products obtained in the substitution reactions of organo(heterocyclic)tellurium(IV) derivatives

The reaction of organo(heterocyclic)tellurium(IV) derivative: C8H8TeI2(1,3-dihydro-2λ4-benzotellurole-2,2-diyl diiodide) with NH4S2CNC5H10 (ammonium piperidine dithiocarbamate) gives C8H8Te(S2CNC5H10)2 (1) and Te(S2CNC5H10)2 (2) or C8H8TeI(S2CNC5H10) (5) according to the reaction conditions. In such type of metathetical reactions, the formation of 2 is unprecedented and it corresponds to the first Te–C cleaved product. The reaction of 2 with CH3I, yields the oxidative addition product, CH3TeI(S2CNC5H10)2 (8). The formation of 2 is also supported through Quantum Chemical calculations. Another Te–C bond cleaved product TeI2[(C13H10N2S)2] · 4C4H8TeI2 (9) is obtained in the reaction of C4H8TeI2 (1,1,2,3,4,5-hexahydro-1,1-diiodotellurophene) with NH4S2CNHC6H5 (ammonium aniline dithiocarbamate). The reaction of 1,1,2,3,4,5,6-heptahydro-1-iodo-1-(morpholine dithiocarbamato) tellurane [C5H10TeI(S2CNC4H8O)] (10) with 1,10-phenanthroline gives an unusual product C12H8N2 · C4H10INO (11). The structures of the new complexes 2, 8, 9, 10 and 11 have been determined by the X-ray analysis.

Reaction of C8H8TeI2 with ammonium piperidine dithiocarbamate gives the usual product C8H8Te(S2CNC5H10)2 (1) and the first Te–C bond cleaved product Te(S2CNC5H10)2 (2). The formation of 2, in such type of substitution reaction, is unprecedented. The reaction of 2 with CH3I yields the oxidative addition product CH3TeI(S2CNC5H10)2 (8). The various postulated processes leading to the formation of 2 are explained through Quantum Chemical calculations. Another Te–C bond cleaved product TeI2[(C13H10N2S)2] · 4C4H8TeI2 (9) is obtained in the substitution reaction of C4H8TeI2 with ammonium aniline dithiocarbamate.Figure optionsDownload as PowerPoint slide