Mono- and bis(dialkyl/aryl dithiocarbamato) complexes of 1,1,2,3,4,5,6-heptahydro-1,1-dihalido telluranes: Synthesis, spectroscopy, structures and cleavage reaction

Reactions of 1,1,2,3,4,5,6-heptahydro-1,1-dihalido telluranes [(C5H10TeX2), X = Cl, Br, I] with sodium/ammonium (dialkyl/aryl dithiocarbamates) viz. NaS2CN(C2H5)2, NH4S2CNC4H8O, NH4S2CNC5H10, NH4S2CNHC6H5 yield new [C5H10TeI{S2CN(C2H5)2} (1), C5H10TeI(S2CNC4H8O) (2), C5H10TeI(S2CNC5H10) (3), C5H10TeBr{S2CN(C2H5)2} (4), C5H10TeBr(S2CNC4H8O) (5), C5H10TeBr(S2CNC5H10) (6), C5H10TeCl{S2CN(C2H5)2} (7), C5H10TeCl(S2CNC4H8O) (8), C5H10TeCl(S2CNC5H10) (9), C5H10TeCl(S2CNHC6H5) (10), C5H10Te{S2CN(C2H5)2}2 (12), C5H10Te(S2CNC4H8O)2 (13), C5H10Te(S2CNC5H10)2 (14)] complexes. The substitution reaction of C5H10TeCl2 with NH4S2CNHC6H5 yields complex (10) along with the cleaved product SC(NHC6H5)2 (11). In such type of substitution reaction, the formation of SC(NHC6H5)2 (11) is uncommon. The probable pathway for obtaining the cleaved product has been postulated on the basis of a comparative account with other similar type of cleavage reactions. The intermolecular Te···S secondary bonds and/or C–H···X (X = O, Cl, I) hydrogen bonds lead to the formation of (stairs, zig-zag ribbons), trimeric, tetrameric, hexameric and decameric supramolecular assemblies. The complexes have been characterized by elemental analysis, IR and (1H, 13C, 125Te) NMR spectroscopy and single crystal X-ray crystallography of 1, 2, 4, 7, 8, 9 and 11.

Graphical abstractMono- and bis dithiocarbamato complexes of heterocyclic (organo)tellurium [C5H10TeI2] supramolecular assemblies involving Te···S secondary bonds and less common C–H···X (X = O, Cl, I) hydrogen bonds are described and probable pathway for obtaining the cleaved product in the substitution reaction is discussed.Figure optionsDownload full-size imageDownload as PowerPoint slide