@phdthesis{Selinka2002,
  author    = {Selinka, Carola},
  title     = {Synthetic routes to asymmetrical Alkylenediimidosulfites and Novel Heteroarene-linked Bis-diimidosulfinates and Bis-triimidosulfonates},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-4271},
  school      = {Universit{\"a}t W{\"u}rzburg},
  year      = {2002},
  abstract  = {This theses deals with the syntheses and the coordination behaviour of polyimidosulfur anions like S(NR)32-, S(NR)42-, RS(NR)2- or RS(NR)3-, the nitrogen analogues of the well known oxo-anions SO32-, SO42-, RSO2- and RSO3-. The first aim was the synthesis of a triimidosulfite with three different NR-substituents, a so called asymmetrical triimidosulfite. In all reactions, that have been carried out to obtain a triimidosulfite with three (or two) different residues at nitrogen, the final product was always the dilithium sulfide adduct. The syntheses of chiral alkylenediimidosulfites was successful. Similar to Corey's S-ylides (R2(O)S+--CR2) and Wittig's phosphonium ylides (R3P+--CR2) these molecules contain a positively charged sulfur atom next to a carbanionic centre. The structures of the alkylenediimidosulfites are not influenced by the different substituents at nitrogen and carbon, respectively. In each case a doublecubic structure is received. The first members of a completely new class of compounds were synthesised: the aryl-bis-(diimidosulfinates). In this compounds two SN2 units are connected via a heteroaromatic linker, containing a potential donor centre in metal coordination. They represent, like the known alkyldiimidosulfinates, dipodal monoanionic ligands. In the field of sulfur (VI) chemistry the syntheses of aryltriimidosulfonates were successful. Hitherto it was believed, that only spatial less demanding lithium organics could be added to a S=N double bond in S(NtBu)3. This assumption was confirmed by the fact that methyl- and phenylacetylene-triimidosulfonate were the only known alkylsulfonates. Nevertheless, the addition of several lithiumheteroarenes to sulfurtriimide worked without difficulties. If the shape of the nucleophile permits to slot in between the NtBu substituents and to approach the electrophilic sulfur in the sulfurtriimide from the side rather than in an orthogonal angle, the addition reaction works smoothly. Although the steric demand of the tris(tert.-butyl)triimidosulfonate unit is very high, the synthesis of thiophene-bis-(triimidosulfonate) worked. The sulfonate moieties function as dipodal ligands.},
  subject      = {Schwefelylide},
  language  = {en}
}