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Thomas M. Klapötke Burkhard Krumm Dieter Naumann 《Journal of fluorine chemistry》2004,125(6):997-1005
The perfluoroaryl tellurolates C6F5TeLi (1) and 4-CF3C6F4TeLi (2) were prepared. These intermediates were identified by NMR spectroscopy and may form, depending on the reaction conditions, either the corresponding ditellanes C6F5TeTeC6F5 (3) and CF3C6F4TeTeC6F4CF3 (4) by subsequent oxidation, or in the case of 1, a telluranthrene (C6F4Te)2 (5) by reaction with itself. The halogenation products of 5, ( C6F4Te)2F4 (6), (C6F4Te)2Cl4 (7), (C6F4Te)2Br4 (8), as well as the azidation product (C6F4Te)2(N3)4 (9) were synthesized. Furthermore, in pursuit of our recent work on tellurium azides, the syntheses and properties of R2Te(N3)2 (R=CF3 (10), C6F2H3 (11)) and RTe(N3)3 (R=CF3 (12) and C6F5 (13)) are reported. The crystal structures of CF3C6F4TeTeC6F4CF3 (4), (C6F4Te)2Br4 (8), and (C6F2H3)2Te(N3)2 (11) were determined. 相似文献
5.
Konstantin Karaghiosoff Thomas M. Klaptke Alexej Michailovski Gerhard Holl 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(9):o580-o581
The title compound (systematic name: 4,10‐dinitro‐2,6,8,12‐tetraoxa‐4,10‐diazatetracyclo[5.5.0.03,11.05,9]dodecane), C6H6N4O8, exhibits the highest density among known N‐nitramines, due to its close‐packed crystal structure. It may be regarded as consisting of a distorted hexagonal close‐packed lattice formed by the isowurtzitane cages, with the nitro groups occupying the free space between the cages. 相似文献
6.
Inis C. Tornieporth-Oetting Thomas M. Klaptke 《Angewandte Chemie (International ed. in English)》1995,34(5):511-520
The chemistry of covalent inorganic azides originated with the synthesis of aqueous HN3 solutions by Tony Curtis in 1890. A little later, in 1900, it proved possible to prepare iodine azide, IN3, as the first member of the meanwhile complete series of halogen azides. Since then it has been possible to synthesize, in addition to HN3 and the stable salt H2NSbF, azide compounds of elements from Groups 13 to 17. In these compounds the N3 moiety acts as a pseudohalogen and is primarily covalently coordinated to the nonmetal. Only a few organic azides, however, as well as HN3, H2N, and all halogen azides have been thoroughly studied with respect to structure and bonding. The combined application of diffraction methods (X-ray and electron diffraction) and microwave spectroscopy together with quantum chemical approaches such as ab initio SCF and density functional calculations have led in the last few years to an improved understanding of the molecular properties of numerous nonmetal azides, almost all of which are explosive. This interaction of theory and experiment has greatly enhanced the development of azide chemistry and has led to realistic expectations for the synthesis of as yet unknown nonmetal azides. 相似文献
7.
The reaction of titanocene dichloride,Cp
2TiCl2 (Cp=5-C5H5), with one or two equivalents of sodium cyanodithioformate affords the new mono- or bis(dithiocarboxylato) derivativesCp
2TiCl(S2CCN) (1) andCp
2Ti(S2CCN)2 (2). Elimination of sulfur converts2 into the metallacyclicCp
2TiS2C2(CN)2 (3), which does not react with the diene isoprene, but can be reconverted into the appropriate titanocene dihalides by chlorine or bromine. 相似文献
8.
The nitration of 5‐amino‐1H‐tetrazole ( 1 ), 5‐amino‐1‐methyl‐1H‐tetrazole ( 3 ), and 5‐amino‐2‐methyl‐2H‐tetrazole ( 4 ) with HNO3 (100%) was undertaken, and the corresponding products 5‐(nitrimino)‐1H‐tetrazole ( 2 ), 1‐methyl‐5‐(nitrimino)‐1H‐tetrazole ( 5 ), and 2‐methyl‐5‐(nitramino)‐2H‐tetrazole ( 6 ) were characterized comprehensively using vibrational (IR and Raman) spectroscopy, multinuclear (1H, 13C, 14N, and 15N) NMR spectroscopy, mass spectrometry, and elemental analysis. The molecular structures in the crystalline state were determined by single‐crystal X‐ray diffraction. The thermodynamic properties and thermal behavior were investigated by using differential scanning calorimetry (DSC), and the heats of formation were determined by bomb calorimetric measurements. Compounds 2, 5 , and 6 were all found to be endothermic compounds. The thermal decompositions were investigated by gas‐phase IR spectroscopy as well as DSC experiments. The heats of explosion, the detonation pressures, and velocities were calculated with the software EXPLO5, whereby the calculated values are similar to those of common explosives such as TNT and RDX. In addition, the sensitivities were tested by BAM methods (drophammer and friction) and correlated to the calculated electrostatic potentials. The explosion performance of 5 was investigated by Koenen steel sleeve test, whereby a higher explosion power compared to RDX was reached. Finally, the long‐term stabilities at higher temperatures were tested by thermal safety calorimetry (FlexyTSC). X‐Ray crystallography of monoclinic 2 and 6 , and orthorhombic 5 was performed. 相似文献
9.
The reaction behavior of NaN3, AgN3, and Me3SiN3 towards FNO2, CINO2, NO2SbF6, and NO2BF4 was investigated. At -30°C or below in a solvent-free system sodium azide did not react with CINO2, NO2BF4, or NO2SbF6. Below -30°C silver azide did not react either with neat C1NO2. Treatment of Me3SiN3 with pure C1NO2 led to the formation of C1N3, N2O, and Me3SiOSiMe3. A mechanism for this reaction has been proposed. Pure chlorine azide was isolated by fractional condensation and identified by its low-temperature Raman spectrum (liquid state). The reaction of Cp2Ti(N3)2 with C1NO2 also yielded C1N3 as the only azide-containing reaction product. Treatment of FNO2 with NaN3 at temperatures as low as -78°C always ended in an explosion which was probably due to the formation of FN3 as one of the reaction products. The reaction of NO2SbF6 with NaN3 in liquid CO2 (-55°C· T· -35°C) as the solvent afforded a new azide species which was stable at low temperature in solution only and was investigated by means of low-temperature Raman spectroscopy. The obtained vibrational data give strong evidence for the presence of tetranitrogen dioxide, N4O2, which can be regarded as nitryl azide (NO2N3). The structure and vibrational frequencies of N4O2 were computed ab initio at correlated level (MP2/6-31 + G*). In liquid xenon (-100°C· T· -60°C) NaN3 did not react with NO2SbF6. A previous literature report on the preparation of N4O2 could not be established. 相似文献
10.
M. Broschag T. M. Klaptke A. Schulz I. C. Tornieporth-Oetting P. Umbach P. S. White 《无机化学与普通化学杂志》1994,620(6):1132-1136
Fluorination of Cyanuric Chloride and Low-Temperature Crystal Structure of [(ClCN)3F]+[AsF6]? The low-temperature fluorination of cyanuric chloride, (ClCN)3, with F2/AsF5 in SO2F2 solution yielded the salt [(ClCN)3F]+ [AsF6]? ( 1 ) essentially in quantitative yield. Compound 1 was identified by a low-temperature single crystal X-ray structure determination: R 3 c, trigonal, a = b = 10.4246(23) Å, c = 15.1850(24) Å, V = 1429.1(4) Å 3, Z = 6, RF = 0.056, Rw = 0.076 (for significant reflections), RF = 0.088, Rw = 0.079 (for all reflections). Fluorination of neat (ClCN)3 with [NF4]+ [Sb2F11]? yielded NF3, CClF3, SbF3, N2 and traces of CF4. A qualitative scale for the oxidizing strength of the oxidative fluorinators NF4+ and (XCN)3F+ (X = H, F, Cl) has been computed ab initio. 相似文献