503027-47-2Relevant 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.
Nitrogen NMR of Some Sulphur Diimide Anions and Calculated (GIAO) Nitrogen Shielding Constants
Wrackmeyer, Bernd,Gerstmann, Silke,Herberhold, Max,Webb, Graham A.,Kurosu, Hiromichi
, p. 492 - 495 (2007/10/02)
Sulphur diimide anions of the type (2-) (1), (-) (1), were prepared with the counter ions (+) or (+) (for 1, 3, 4) and K(+) (for 5) and studied in solution by 14N NMR, and for assignment purposes by 15N NMR (4).The experimentally determined 14N chemical shifts (δN) were compared with nitrogen shielding constants calculated by the gauge included atomic orbitals (GIAO) technique, and a linear relationship between ?N(calc) and δN was obtained.This correlation serves to support the Z configuration of the anions (-), analogous to the isoelectronic N-sulphinylamines.On the basis, two 14N resonance signals reported in the literature with uncertain assignment can be attributed to (-) (2), and the previously assigned δN values suggest that the anion (-) (6) adopts the Z/E configuration. - Keywords: Sulphur diimide anions Configuration 14N NMR 15N NMR Nitrogen shielding GIAO calculation
Cyclic Sulfur Diimides of Silicon. (15)N NMR Spectroscopy and the X-Ray Analysis of the Eight-Membered Ring tBu2Si(NSN)2SitBu2
Herberhold, Max,Gerstmann, Silke,Milius, Wolfgang,Wrackmeyer, Bernd
, p. 1041 - 1050 (2007/10/02)
Various six-membered cyclic sulfur diimides (3a-f) were prepared by aminolysis of the bis(chloro-dimethylsilyl)sulfur diimide (2) using NH3 (a) and primary amines RNH2 nPr (d), nBu (e), iPr (f)>.Except for R = H, non-cyclic intermediates, the Si-monoamino- (7) and Si,Si'-diamino derivatives of 2 (8), were detected for all groups R, including R = tBu (g).The reaction between R2SiCl2 and the sulfur diimide anion K gave non-cyclic silanes (9,10) and the eight-membered rings of the type R2Si(NSN)2SiR2 tBu (5)> of which 5 was studied by X-ray analysis (monoclinic, space group P21/c; planar ring system) and solid-state (15)N and (29)Si CP/MAS NMR spectroscopy.The ten-membered ring system 6 was obtained from the reaction between 1,2-dichloro-tetramethyldisilane and bis(trimethylstannyl)sulfur diimide.All compounds were studied by (1)H, (13)C, (15)N and (29)Si NMR.The δ(15)N NMR data proved useful to distinguish between fluxional systems with fast E/Z-Z/E isomerization (non-cyclic compounds 8 and the ten-membered cycle 6).Hahn-Echo-extended (HEED) polarization transfer (INEPT) pulse sequences served to measure coupling constants 1J((29)Si(15)Namine) for the compounds 3 and 8.This also proved that the magnitude of 1J((29)Si(15)NNSN) must be small (1J((29)Si(15)Namine) and 1J((15)N(1)H) (3a) indicated that the amino-nitrogen atom adopts a pyramidal environment.
