Jump to main content
Jump to site search


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(NtBu)2]Li) having a phenyl group on the sulphur atom with ECl2·(dioxane) (E = Ge, Sn) afforded the corresponding chlorogermylene [PhS(NtBu)2]GeCl 1 and -stannylene [PhS(NtBu)2]SnCl 2, respectively. In contrast, treatment of 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)211-GeCl)2[μ-NSPh(NHSiMe3)] 7 and -stannylene [PhS(NSiMe3)2(η11-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-η11-fashion. As reactivity of 1 and 2, oxidation of 1 with elemental chalcogen (S8 or Se) afforded the corresponding tetra-coordinated germanium compounds [PhS(NtBu)2]Ge(=Ch)Cl 3 (Ch = S) and 4 (Ch = Se). 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(NtBu)2]GeCl(μ-Ch)}25 (Ch = S) and 6 (Ch = Se).

Back to tab navigation

Supplementary files

Publication details

The article was received on 21 Nov 2017, accepted on 29 Nov 2017 and first published on 30 Nov 2017


Article type: Paper
DOI: 10.1039/C7DT04390B
Citation: Dalton Trans., 2017, Accepted Manuscript
  •   Request permissions

    Chlorogermylenes and -Stannylenes Stabilized by Diimidosulfinate Ligands: Synthesis, Structures, and Reactivity

    N. Nakata, N. Hosoda, S. Takahashi and A. Ishii, Dalton Trans., 2017, Accepted Manuscript , DOI: 10.1039/C7DT04390B

Search articles by author

Spotlight

Advertisements