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 [(C(5)H(10)TeX(2)), X = CI, Br, I] with sodium/ ammonium (dialkyl/aryl dithiocarbamates) viz. NaS(2)CN(C(2)H(5))(2), NH(4)S(2)CNC(4)H(8)O, NH(4)S(2)CNC(5)H(10). NH(4)S(2)CNHC(6)H(5) yield new [C(5)H(10)Tel(S(2)CN(C(2)H(5))(2)) (1), C(5)H(10)Tel(S(2)CNC(4)H(8)O) (2), C(5)H(10)Tel(S(2)CNC(5)H(10)) (3), C(5)H(10)TeBr(S(2)CN(C(2)H(5))(2)) (4). C(5)H(10)TeBr(S(2)CNC(4)H(80)) (5), C(5)H(10)TeBr(S(2)CNC(5)H(10)) (6), C(5)H(10)TeCIl{S(2)CN(C(2)H(5))(2)) (7). C(5)H(10)TeCI(S(2)CNC(4)H(80)) (8), C(5)H(10)TeCI(S(2)CNC(5)H(10)) (9). C(5)H(10)TeCI(S(2)CNHC(6)H(5)) (10), C(5)H(10)Te(S(2)CN(C(2)H(5))(2))(2) (12), C(5)H(10)Te(S(2)CNC(4)H(8)O)(2) (13), C(5)H(10)Te(S(2)CNC(5)H(10))(2) (14)] complexes. The substitution reaction of C(5)H(10)TeCl(2) with NH(4)S(2)CNHC(6)H(5) yields complex (10) along with the cleaved product SC(NHC(6)H(5))(2) (11). In such type of substitution reaction, the formation of SC(NHC(6)F(15))(2) (S)parallel to(H5C6HN-C-NHC6H5) (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 center dot center dot center dot S secondary bonds and/or C-H center dot center dot center dot 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 ((1)H, (13)C, (125)Te) NMR spectroscopy and single crystal X-ray crystallography of 1, 2, 4, 7, 8, 9 and 11. (C) 2010 Elsevier Ltd. All rights reserved.