Synthesis and thermal decomposition studies of homo- and heteroleptic tin(IV) thiolates and dithiocarbamates: Molecular precursors for tin sulfides

The syntheses and X-ray structures of novel heteroleptic thiolate/dithiocarbamate derivatives (Et2NCS2)2(RS)2Sn (R = Cy, CH2CF3) have been examined and their thermal decompositions compared with those of selected tin(II) and tin(IV) dithiocarbamates. The heteroleptic species decompose to SnS by initial elimination of RSSR to afford (Et2NCS2)2Sn and subsequent loss of [Et2NC(S)]2S. In contrast, (Et2NCS2)4Sn decomposes via [(Et2NCS2)2SnS]2, whose structure has been determined, and finally to SnS2 by sequential elimination of [Et2NC(S)]2S. The two families of compounds, (R2NCS2)4Sn and (Et2NCS2)2(RS)2Sn, thus provide single-source materials for bulk SnS2 and SnS, respectively, by virtue of their differing decomposition pathways. Preliminary CVD experiments with (Et2NCS2)2(CyS)2Sn are also reported.