Chlorogermylenes and -stannylenes stabilized by diimidosulfinate ligands: synthesis, structures, and reactivity

Abstract

The reaction of the lithium salt of N,N′-di-tert-butyldiimidosulfinate ([PhS(N^tBu)₂]Li) having a phenyl group on the sulphur atom with ECl₂·(dioxane) (E = Ge, Sn) afforded the corresponding chlorogermylene [PhS(N^tBu)₂]GeCl 1 and -stannylene [PhS(N^tBu)₂]SnCl 2, respectively. In contrast, treatment of the N,N′-bis(trimethylsilyl)diimidosulfinate ion ([PhS(NSiMe₃)₂]⁻) with ECl₂·(dioxane) resulted in the unexpected formations of six-membered 1,3-bis(chlorogermylene) [PhS(NSiMe₃)₂(η¹-η¹-GeCl)₂[μ-NSPh(NHSiMe₃)] 7 and -stannylene [PhS(NSiMe₃)₂(η¹-η¹-SnCl)₂[μ-NSPh(NHSiMe₃)] 8. The structures of these chlorometallylene derivatives were fully characterized on the basis of their NMR spectroscopic data and X-ray diffraction. In the crystalline states of 1 and 2, the diimidosulfinate ligands chelate to the metal centre to form slightly hinged four-membered EN₂S rings. On the other hand, X-ray analyses of 7 and 8 revealed that the central six-membered E₂N₃S rings adopt a distorted boat-conformation, and one diimidosulfinate ligand coordinates to the metal centre in a bridging monodentate μ–η¹–η¹-fashion. As the reactivity of 1 and 2, the oxidation of 1 with elemental chalcogen (S₈ or Se) afforded the corresponding tetra-coordinated germanium compounds [PhS(N^tBu)₂]Ge(Ch)Cl 3 (ChS) and 4 (ChSe). In sharp contrast, the reactions of 2 with elemental chalcogen resulted in the formation of four-membered Sn₂Ch₂ ring compounds, 1,3,2,4-dichalcogenadistannetanes {(PhS(N^tBu)₂)SnCl(μ-Ch)}₂5 (ChS) and 6 (ChSe).