7522-26-1Relevant articles and documents
Preparation, characterisation, quantum chemical calculations, and chemical reactions of sulfurdiimine, its silver and thallium salts as well as TlNSO
Haas, Alois,Fleischer, Ulrich,Maetschke, Matthias,Staemmler, Volker
, p. 681 - 692 (2008/10/08)
Reactions of (CH3)3SiNSNSi(CH3)3 with Ag[CF3C(O)O] or TlF respectively have allowed the formation of the highly explosive compounds M2[SN2] (M = Ag, Tl) in nearly quantitative yields. Under analogous conditions (CH3)3SiNSO and TlF formed non-explosive TlNSO again in about 100% yield. The reaction between (CH3)3SiNSNSi(CH3)3 and ICl was found to be easily reproducable and gave INSNI in good yields. INSNI was obtained also from K2[SN2] and ICl in 40% yield. The reaction of (CH3)3SiNSNSi(CH3)3 with CsF resulted in monosubstitution and the formation of CsNSNSi(CH3)3. INSNI reacted with HX (X = Cl, I) in closed systems to give S4N4, NH4X, IX and N2 as final products. Similar results were observed when M2[SN2] was treated with HX in Carius tubes. Besides higher yields of S4N4 small amounts of S4N3Cl and other not identified SN compounds were detected. In open systems HX reacted with M2[SN2] in dynamic vacuo explosively. Under matrix conditions preliminary tests showed that TlNSO formed with HX pure HNSO, characterised by a high quality matrix IR-spectrum. With the help of this metathetical reaction, the conditions for matrix-spectroscopic studies of the system MNSNM and HX could be optimized. If M2[SN2] was treated with HX analogously HNSNH was produced. The diimine was characterized by bands of comparable intensities, appearing in spectra of the products of the reaction which were assigned to the molecule. Identical bands were also observed when INSNI was treated with excess HX. If the procedure was carried out with 1:1 molar quantities, the formation of the primary produced HNSNI could be evidenced by IR-spectroscopy. Detailed quantum chemical ab inition calculations about structures, relative energies and vibrational spectra of the HNSNH-conformers as well as other possible SN2H2 isomeres were carried out. They confirmed the experimental results and assignments and strengthened the conclusion that HNSNH was present as a mixture of E,Z- and Z,Z-conformers.
