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

Abstract

Reactions of 1,1,2,3,4,5,6-heptahydro-1,1-dihalido telluranes [(C 5H 10TeX 2), X = Cl, Br, I] with sodium/ammonium (dialkyl/aryl dithiocarbamates) viz. NaS 2CN(C 2H 5) 2, NH 4S 2CNC 4H 8O, NH 4S 2CNC 5H 10, NH 4S 2CNHC 6H 5 yield new [C 5H 10TeI{S 2CN(C 2H 5) 2} ( 1), C 5H 10TeI(S 2CNC 4H 8O) ( 2), C 5H 10TeI(S 2CNC 5H 10) ( 3), C 5H 10TeBr{S 2CN(C 2H 5) 2} ( 4), C 5H 10TeBr(S 2CNC 4H 8O) ( 5), C 5H 10TeBr(S 2CNC 5H 10) ( 6), C 5H 10TeCl{S 2CN(C 2H 5) 2} ( 7), C 5H 10TeCl(S 2CNC 4H 8O) ( 8), C 5H 10TeCl(S 2CNC 5H 10) ( 9), C 5H 10TeCl(S 2CNHC 6H 5) (1 0), C 5H 10Te{S 2CN(C 2H 5) 2} 2 ( 12), C 5H 10Te(S 2CNC 4H 8O) 2 ( 13), C 5H 10Te(S 2CNC 5H 10) 2 ( 14)] complexes. The substitution reaction of C 5H 10TeCl 2 with NH 4S 2CNHC 6H 5 yields complex ( 10) along with the cleaved product SC(NHC 6H 5) 2 ( 11). In such type of substitution reaction, the formation of SC(NHC 6H 5) 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.