503027-47-2Relevant academic research and scientific papers
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.
Sulfur diimides bearing dialkylboryl and bis(amino)boryl substituents-studied by multinuclear magnetic resonance spectroscopy
Herberhold, Max,Gerstmann, Silke,Wrackmeyer, Bernd
, p. 255 - 277 (2007/10/03)
Reactions of metallated sulfur diimides, K(NSN)R (R = tBu, SiMe3, PtBu2) and K(NSN)K, with various boron chlorides R12,BCl (R1 = tBu, cpent, Et2N, iPr2N), [CH2N(R1)]2BCl (Rl = Me, nBu, lPr, tBu) and R1R2NBCl2 (R1 = R2 = Et, iPr ; R1 = PhCH2, R2 = tBu; R1 = PhCH2, R2 = Ph) lead to the corresponding boryl-substituted sulfur diimides 2 - 8, 9a -20a, 9b, 11b - 13b, 17b and 15c.The sulfur diimides (Et2N)2B(NSN)SiMe3 (11b) and (iPr2N)2B(NSN)tBu (12a) react with hexachlorodisilane by cleavage of the Si-Si bond to give the new bis(amino)sulfanes 21b and 22a, in which the nitrogen atoms bear additional SiCl3 substituents. A complete NMR spectroscopic study was carried out for the known cyclic sulfur diimide iPr2B(NSN)2BNiPr2 (1). All non-cyclic compounds were studied by 1H, 11B, 13C and 15N NMR at variable temperature aiming for configurational assignment. The 15N NMR data, in particular, suggest that in most cases almost linear N=S-B units are preferred with a perpendicular arrangement of the plane of the boryl group with respect to the NSN plane.
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
Solid-state Structure of Sulfur Bis(trimethylsilylimide), S(NSiMe3)2, and Multinuclear Magnetic Resonance Studies of Some Sulfur Bis(silylimides) in Solution
Herberhold, Max,Gerstmann, Silke,Wrackmeyer, Bernd,Borrmann, Horst
, p. 633 - 636 (2007/10/02)
In the solid state sulfur bis(trimethylsilylimide) 1 has been shown to adopt the E/Z configuration by single-crystal X-ray diffraction (space group P, triclinic).In solution sulfur bis(silylimides) R(NSN)R' are fluxional at room temperature.Comparison of the 1H, 13C, 29Si and, in particular, 15N NMR data indicates that 1 and 2 undergo rapid E/Z Z/E isomerization even at 173 K, whereas in the case of 3 and 4 this process is slowed at low temperature and the E/Z configuration prevails with the SiMe3 group in the E position.
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.
REACTIONS OF α,α,ω-TRIHYDROPOLYFLUOROALKOXYTRIFLUOROSULFURANES WITH PRIMARY AMINES AND AMIDES
Markovskii, L.N.,Tovstenko, V.I.,Pashinnik, V.E.,Mel'nichuk, E.A.,Makarenko, A.G.,Shermolovich, Yu.G.
, p. 660 - 663 (2007/10/02)
α,α,ω-Trihydropolyfluoroalkoxytrifluorosulfuranes react with primary amides or their N,N'-di(trimethylsilyl) derivatives to form acid fluoride derivatives of N-substituted polyfluoroalkyliminosulfurous acids.The thermal stability of these products depends
SYNTHESIS OF EXTENDED ACYCLIC AZATHIENES WITH AROMATIC SUBSTITUENTS. III. PHTHALIMIDO GROUP AS THE LEAVING GROUP
Zibarev, A. V.,Miller, A. O.,Shakirov, M. M.,Furin, G. G.
, p. 864 - 872 (2007/10/02)
The use of the phthalimido group as the leaving group makes it possible to obtain asymmetric 1,7-diaryl-1,3,5,7-tetraaza-2,4,6-trithia-1,2,5,6-heptatetraenes, which are not obtainable by the previously known methods.Cesium fluoride in acetonitrile increases the nucleophilicity of the nitrogen atom of the N-trimethylsilyl derivatives of acyclic azathienes and phthalimide.In acetonitrile solution a spontaneous shortening of the sulfur-nitrogen chain of 1,7-bis(trimethylsilyl)-1,3,5,7-tetraaza-2,4,6-trithia-1,2,5,6-heptatetraene takes place.
Heterocyclic 1,2,4,6-Thia- and 1,2,4,6-Selenatriazinyl radicals. Spin distributions and modes of association
Bestari, Ketut,Cordes, A. Wallace,Oakley, Richard T.,Young, Kelly M.
, p. 2249 - 2255 (2007/10/02)
Synthetic routes to the heterocyclic 1-chloro-1,2,4,6-thia- and -selenatriazines [(Ph2P)2-x(PhC)xN3ECl] (x = 0, 1; E = S, Se) have been developed. For x = 0 the method involves the coupling of [ClPh2P
Gas-phase Molecular Structure of N,N'-Bis(trimethylsilyl)sulphur Di-imide, determined by Electron Diffraction
Anderson, David G.,Robertson, Heather E.,Rankin, D. W. H.,Woollins, J. Derek
, p. 859 - 862 (2007/10/02)
The molecular geometry of Me3SiNSNSiMe3 in the gas phase has been studied by electron diffraction.The molecule has C2 symmetry with a distorted syn,syn conformation.Principal parameters are : ra(S=N) 153.6(3), ra(Si-N) 173.8(3), and ra(Si-C) 186.9(1) pm; NSN 129.5(16), SNSi 132.9(7), and SN twist (relative to syn,syn conformation) 42(1) deg.
