- A μ-1,1,1,3,3,3 azide anion inside a trigonal prism of silver centers
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Layers of face- and edge-sharing trigonal Ag6 prisms, of which half are filled with azide units, are contained in the novel compound AgN3 · 2AgNO3 (see structure). Pendant η1-nitrate groups are attached to both sides of each layer.
- Guo, Guo-Cong,Mak, Thomas C. W.
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- A new route to metal azides
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Beside several other applications, metal azides can be used for the synthesis of nitridophosphates and binary nitrides. Herein we present a novel synthetic access to azides: Several metals, such as main-group, transition metals, and rare-earth metals, react with silver azide in liquid ammonia as a solvent giving the corresponding metal azides. In this work Mn(N3)2, Sn(N3)2, and Eu(N3)2, as well as their ammonia complexes were synthesized for the first time through low- temperature methods. Also a simpler access to Zn(N3)2 was possible. At room temperature and the respective vapor pressure of NH3, it became possible to grow single crystals of the dinuclear holmium azide [Ho2(m-NH2)3-(NH3)10](N3)3·1.25NH3. We are confident that this new route could lead to novel metal azides as well as nitrides of the main-group, the transition, and the rare-earth metals upon careful decomposition.
- Müller, Thomas G.,Karau, Friedrich,Schnick, Wolfgang,Kraus, Florian
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- Binary polyazides of cadmium and mercury
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Following our interest in binary element-nitrogen compounds we report here on the synthesis and comprehensive characterization (M.p., IR/Raman, elemental analysis, 14N/133Cd/199Hg NMR) of tri-and tetraazido cadmate and mercurate anions [E(N3)(2+n)]n- (E = Cd, Hg; n = 1, 2) in a series of [Ph4P]+ and [PNP]+ ([PNP]+ = bis(triphenylphosphine)-iminium) salts. The azide/chloride exchange in CH2Cl2 as well as the formation of tetrazolate salts in CH3CN solutions of the polyazido mercurates were investigated. Single crystal X-ray structures of all new compounds, and for comparison [Ph4P][Cd2(N3)5(H2O)], were determined. Moreover, the synthesis of anhydrous cadmium(II) azide and its DMSO adduct is presented for the first time. For a better understanding of structure and bonding in E(N3)2, [E(N3)3]- and [E(N3)4]2-, theoretical calculations at the M06-2X/aug-cc-pVDZ level were carried out.
- Schulz, Axel,Villinger, Alexander
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- Synthesis and characterization of N,N′,C-bound organotellurium(IV) and organomercury(II) derivatives
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We report the synthesis and characterization of the first examples of organotellurium (IV)/organomercury(II) derivatives of N,N′,C-chelating aryldiamine ligand, 2-{Me2NCH2CH2N(Me)CH2}C6H4Br (20). The dichalcogenides, [2-{Me2NCH2CH2N(Me)CH2}C6H4Se]2 (24) and [2-{Me2NCH2CH2N(Me)CH2}C6H4Te]2 (25), were prepared by treatment of the corresponding Grignard reagent (21)/organolithium reagent (22) in THF with selenium or tellurium, respectively. Compounds [2-{Me2NCH2CH2N(Me)CH2}C6H4]2Se (26) and [2-{Me2NCH2CH2N(Me)CH2}C6H4]Te(S2CN(CH2CH3)2 (27) were synthesized by the reaction of 21/22 with Se(dtc)2 in 2:1 or Te(dtc)2 (dtc = diethyldithiacarbamate) in 1:1 ratio at room temperature. In contrast, the reaction of 21 with TeI2 afforded an unexpected protonated derivative, [2-{(Me2NH)CH2CH2N(Me)CH2}C6H4TeI]+(I)? (28a). Similarly, the halogenation reactions of 25 with chlorine gas or a solution of bromine in THF afforded protonated derivatives, [2-{(Me2NH)CH2CH2N(Me)CH2}C6H4TeCl3]+(Cl)? (29a) and [2-{(Me2NH)CH2CH2N(Me)CH2}C6H4TeBr3]+(Br) ? (30a), respectively. The organomercury precursors; 2-{Me2NCH2CH2N(Me)CH2}C6H4HgCl0.54/Br0.46 (31) and 2-{Me2NCH2CH2N(Me)CH2}C6H4HgBr (32), were obtained by the reaction of 21 with HgCl2 and HgBr2 in dry THF, respectively. The metathetical reaction of 31with silver azide afforded air- and moisture-stable organomercury azide, 2-{Me2NCH2CH2N(Me)CH2}C6H4HgN3 (33) in 87% yield. The transmetallation reaction of 31 with TeBr4 led to isolation of known o-formylphenyltellurenyl bromide. All the derivatives were characterized by various spectroscopic techniques such as 1H, 13C, 77Se, 125Te, 199Hg NMR spectroscopy, elemental analysis, ES-MS and HRMS studies.
- Singh, Puspendra,Gupta, Anand K.,Sharma, Sagar,Singh, Harkesh B.,Butcher, Ray J.
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- New gas phase reaction to iodine azide, IN3: Microwave spectrum and structure
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The unstable molecule iodine azide has been prepared for the first time by a gas phase reaction in a flow system, and the microwave spectra of two isotopic species, a- and b-type, have been measured: the abundant species in the frequency range from 10 to 40GHz, the I14N15N 14N-species from 20 to 26GHz. Rotational constants and centrifugal distortion parameters were obtained. The molecule has been shown to be planar, and the structure was derived. Also, the I-quadrupole coupling constants have been determined.
- Munz,Bodenseh,Ferner
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- Synthesis of sub-micron silver and silver sulfide particles via solvothermal silver azide decomposition
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Many transition-metal azides are thermodynamically unstable with respect to the elements and thus, may serve as energetic precursor sources in nanoscale metal particle synthesis. This report describes the use of silver azide (AgN3) in nonaqueou
- Grocholl, Luke,Wang, Jianjun,Gillan, Edward G.
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- Solid state structure of Bi(N3)3, Bi(N 3)3·solvates and the structural dynamics in the [Bi(N3)6]3- anion
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The highly explosive bismuth triazide, Bi(N3)3, was obtained in pure form by the reaction of BiF3 with Me 3SiN3 in acetonitrile under solvothermal conditions at temperatures between 90 and 100 °C. X-ray, 14N NMR, infrared, and Raman spectra are discussed along with the data for the acetonitrile, acetone, and dmso adducts. The influence of the solvent on the purity of the azide products is studied in detail for Bi(N3)3 and the [Bi(N3)6]3- ion. Moreover, temperature dependent structural dynamics in the [Bi(N3)6] 3- ion, which is caused by small changes in the local environment around the [Bi(N3)6]3- ion in the solid state, was studied by temperature variable single crystal X-ray and Raman studies. The azido-chlorido ligand back exchange was studied in detail by NMR techniques in [Bi(N3)6]3- and Bi(N3)3 when chlorinated solvents such as CH2Cl2 were utilized leading to the formation of CH2(N3)Cl and/or HN 3 along with partially chlorinated bismuth azides.
- Rosenstengel, Kati,Schulz, Axel,Villinger, Alexander
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supporting information
p. 6110 - 6126
(2013/07/05)
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- The rules governing the formation of silver azide photolysis products
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Irradiation of silver azide at λ = 365 nm (I > 1 × 10 15 quantum cm-2 s-1) in a avcuum (1 × 10-5 Pa) leads to an increase in the rate of photolysis and photoinduced current and the appearance of a new long-wave region of spectral sensitivity. The photolysis products, silver metal and gaseous nitrogen, are formed in a stoichiometric ratio on the surface of silver azide. The rate constants for silver azide photolysis were determined. Measurements of contact potential difference, current-voltage characteristics, photoelectromotive force, and photocurrent showed that AgN3(A1)-Ag (photolysis product) microheterogeneous systems were formed in silver azide photolysis. The limiting stage of silver azide photolysis is the diffusion of interstitial silver cations to the (TnAg m )0 neutral center.
- Surovoi,Sirik,Bugerko
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p. 292 - 297
(2008/04/06)
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- Synthesis and structures of triorganotelluronium pseudohalides
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The syntheses of [(CH3)3Te]X {X = N3 (1), OCN (2), SCN (3), SeCN (4), [Ag(CN)2] (5)} and [(C6H5)3Te]X {X = N3 (6), SeCN (7), [Ag(CN)2] (8)}, their NMR spectroscopic data, vibrational spectra and single crystal structures are described. Compounds 1-4 are the first trimethyltelluronium pseudohalides, while the known compounds 6 and 7 have been prepared for completion of their analytical and structural properties. The occurrence of intermolecular Te···N, Te···O, Te···S and Te···Se contacts is thoroughly studied. The dicyanoargentates 5 and 8 were obtained in an attempt to prepare telluronium cyanides. Low-temperature 13C NMR spectroscopy of the [Ag(CN)2]- ion in solution has been carried out, with determination of the 13C-107/109Ag coupling. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
- Klapoetke, Thomas M.,Krumm, Burkhard,Mayer, Peter,Piotrowski, Holger,Schwab, Ingo,Vogt, Martin
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p. 2701 - 2709
(2007/10/03)
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- Molybdenum Complexes of Bioinorganic Interest: Studies on the Bonding Mode of Cyanate and Azide Ions in (py)4M4X2MoS4 and (phen)2M4X2MoS4 (M=CuI or AgI; X=OCN- or N3-)
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Molybdenum complexes, (py)4M4X2MoS4 and (phen)2M4X2MoS4 (M=CuI, AgI; X=OCN- or N3-), have been synthesised and characterised by elemental analysis, molar conductance, magnetic moment, infrared and electronic spectral studies.End-to-end azide bridging for the azide complexes and oxygen-bonded cyanate terminals for the cyanate complexes have been proposed.The values of quantitative softness of metals (En) and ligands (Em) have been found to support the proposed structure of the complexes.
- Sharma, S. B.,Tewari, I. N.
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p. 714 - 718
(2007/10/02)
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- Kinetics and mechanism of silver(III) reduction by azide ion in aqueous alkaline media
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The reaction between the tetrahydroxoargentate(III) ion and azide ion proceeds via formation of a monoazidosilver(III) complex, which undergoes internal two-electron redox only after reaction with an additional N3-. Formation of Ag(OH)3N3- from Ag(OH)4- and N3- obeys the full rate law for for reversible associative substitution by both solvent and ligand paths. Two parallel paths also occur in the redox step, both requiring adjacent azide groups prior to electron transfer. Final products are Ag(I) and N2. Three kinetic determinations of the equilibrium constant for Ag(OH)3N3- are in reasonable agreement with the value of 0.38 ± 0.14 obtained spectrophotometrically (25°C, μ = 1.2 M). The result that the nucleophilicity of N3- toward Ag(III) is slightly less than that of OH- is in agreement with previous observations for isoelectronic Pd(II).
- Borish, Edward T.,Kirschenbaum, Louis J.
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p. 2355 - 2359
(2008/10/08)
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- Chemical Processes in the Dissolution of Irradiated Silver Azide
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The chemical processes occurring on dissolution of irradiated AgN3 in aqueous ammonia, Na2S2O3, and dilute HNO3 solutions have been investigated.The development reaction, leading to an increase in the size of the particles, has been observed on small radiolytic silver particles.The characteristics of this process have been determined and the dimensions of the developed particles have been estimated.
- Ryabykh, S. M.,Konovalova, F. I.
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p. 1500 - 1502
(2007/10/02)
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