Sulfur-nitrogen cations and anions

Numerous charged sulfur-nitrogen species have been synthesized in recent years, particularly those having an odd number of N atoms which would otherwise be paramagnetic. However, thio analogues of nitrites (N02, p. 461) and nitrates (N03, p. 465) are unknown. 

The cation has considerable synthetic potential for a wide range of S/N compounds, 

Thionitrosyl complexes have already been briefly mentioned on p. 453 and have recently been reviewed.They were first made by reacting azido complexes directly with 

WooLLiNS, Chap. 18 in R. Steudel (ed.). The Chemistry of Inorganic Ring Systems, Elsevier, Amsterdam, 1992, pp. 349-72. 

The radical cation S3N2 is formed in high yield from the oxidation of S4N4 with the anhydride (CF3S02)204 38) 

---

Sulfur-Nitrogen Cations and Anions. The simple cation, NS2, is the analogue of the nitronium (N02) ion it is made by the reaction ... 

Free radical rearrangements 6 Nitrogen-centered radicals 7 Nitroxyl radicals 7 Aryloxy radicals 8 Sulfur-centered radicals 8 Ketyl radicals 9 Radical cations and anions 10... 

Sulfur and nitrogen exhibit versatile behaviour in the formation of binary cations, anions, and neutral molecules. Those species which have been structurally characterized by X-ray crystallography are listed in Table 1. In order to emphasise the recent progress of the subject of sulfur-nitrogen chemisti, the following developments should be noted a) Seven of the eight known cations have been discovered and... 

Like sulfur mustard, the nitrogen mustards combine predominantly with the thiol group of molecules and are excreted as conjugated cysteinyl derivatives. Both nitrogen and sulfur mustards have structural similarities and have common chemical reactions. A key reaction is the intramolecular cyclization in a polar solvent such as water to form a cyclic onium cation and a free anion. Nitrogen mustards form the immonium cation, while the sulfur mustard forms the sulfonium cation. The cyclized form is responsible for the varied effects of mustards, which are similar. In nitrogen mustard the sulfur is replaced by nitrogen. 

---