Chalcogen-Nitrogen Halides

Thiazyl fluoride is a moisture-sensitive, thermally unstable gas.88 It is conveniently generated by decomposition FC(0)NSF2 or Hg(NSF2)2- It forms the cyclic trimer (NSF)3 at room temperature. 

Thiazyl halide monomers undergo a variety of reactions that can be classified under the general headings (a) reactions involving the 7i-system of the N = S triple bond, (b) nucleophilic substitution, (c) halide abstraction, and (d) halide addition. The cycloaddition of NSF with hexafluoro-1,3-butadiene provides an example of a type (a) reaction. 

Selenazyl halides NSeX have not been characterized either as monomers or cyclic oligomers. However, the monomeric ligand is stabilized in metal complexes of the type [MCl4(NSeCl)]2 (M=Mo, W)94 

Thiazyl trifluoride, a colourless gas, is prepared by the oxidative decomposition of FC(0)NSF2 with AgF2.95 The chemical inertness of NSF3 resembles that of SF6. For example, it does not react with sodium metal below 200 °C. 

Nucleophilic reagents such as secondary amines, alcohols or organolithium reagents convert NSF3 into monosubstituted derivatives NSF2R (R=R 2N, R O, Ar) with retention of the N = S bond.162 

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The reaction of Me3SiNSNSiMc3 with TeCU is an especially fruitful source of chalcogen-nitrogen halides that contain both sulfur and tellurium. The initial product of this reaction is the bicyclic compound 8.17, which is obtained when the reaction is carried out in a 1 2 molar... 

Chalcogen-Nitrogen Halides Containing Three-Coordinate Nitrogen... 

The acyclic imidoselenium(II) dihalides ClSe[N( Bu)Se]nCl (8.23, n =1 8.24, n = 2) are obtained from the reaction SeCla with tert-butylamine in a 2 3 molar ratio in THF. There are no sulfur or tellurium analogues of this class of chalcogen-nitrogen halide. 

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