Organotin(IV) azepane dithiocarbamates: Synthesis and characterization of the first organotin(IV) complexes with seven-membered cyclic dithiocarbamates

摘要

We report the synthesis and spectroscopic characterization of the first organotin(IV) complexes with cyclic seven-membered dithiocarbamate ligands: the azepane-1-carbodithioate and the homopiperazine-1,4-bis-carbodithioate with two different organotin entities, di-n-butyltin and tri-cyclohexyltin: [(C4H9)(2)Sn{S2CN(CH2)(6)}(2)] (3), [(C6H11)(3)Sn{S2CN(CH2)(6)}] (4), and [(C6H11)(3)Sn}(2) (mu-S2CN(C5H10)NCS2)] (5). Compounds (3-5) are air-stable both in solid-state and in solution, and were characterized by elemental analyses, IR, FAB(+)-MS, and multinuclear NMR (H-1, C-13, and Sn-119) spectroscopy. Their molecular structures were unambiguously established by single-crystal X-ray diffraction studies. The geometrical arrangement around the tin atom can be described as distorted octahedral for (3) and distorted trigonal bipyramid for (4) and (5). The coordination mode for both ligands is considered as asymmetric bidentate, as happens in other organotin(IV) dithiocarbamates. Furthermore, (4) and (5) do not exhibit intermolecular secondary interactions, while (3) presents intermolecular interactions between the tin and a sulfur atom with the reciprocally neighboring molecule, giving rise to a zig-zag polymeric structure.