Antimony and bismuth dithiocarboxylates: Synthesis, characterization, crystal structures of [Sb(S_2Cto1)_3] and [Bi(S_2CPh)_3] and their transformation to polycrystalline M_2S_3 (M = Sb, Bi)

摘要

Antimony and bismuth dithiocarboxylates of the type [M(S_2CAr)_3] (M = Sb, Bi; Ar = C_6H_5 (Ph), 4-MeC_6H_4 (tol)) have been synthesized. These complexes were characterized by elemental analysis, IR, UV-Vis, and ~1H NMR spectroscopy. X-ray crystal structural analyses of [Sb(S_2Cto1)_3] and [Bi(S_2CPh)_3] showed that the dithiocarboxylates are asymmetrically chelated,to metal atom. The latter acquires a distorted pentagonal pyramidal geometry as a consequence of the presence of a stereochernically active lone pair of electrons. Pyrolysis of these complexes either in a furnace or in refuxing diphenylether gave M_2S_3 as characterized by their XRD pattern and EDAX analysis.