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1.
Reactions of Formic Acid Methylester in the Super Acidic System XF/MF5 (X = H, D: M = As, Sb) and the Crystal Structure of HC(OH)(OCH3)+AsF6 The reaction of formic acid methyl ester in the superacidic system XF/MF5 (X = H, D: M = As, Sb) leads to the hydroxy methoxy carbenium hexafluorometallates. The very hydrolysable and thermo labile salts are characterized by vibrational and NMR spectroscopic methods. Under inert conditions they are stable at –20 °C for some weeks. HC(OCH3)(OH)+AsF6 crystallizes in the monoclinic space group P21/c (No. 14) with a = 5.275(1) Å, b = 11.059(1) Å, c = 12.113(1) Å und β = 96.64(1)° and four formula units per cell.  相似文献   

2.
Preparation of the Iminium Salts CF3? NX?CF2+MF6? (X = CH3, F and M = As, Sb) and CF3? NCl?CF2+ AsF6? The preparation of the iminiumsalts CF3? NX?CF2+ MF6? (X = CH3, F and M = As, Sb) and CF3? NCl?CF2+ AsF6? is reported. The salts were characterized by NMR and infrared spectroscopy. CF3? NCH3?CF2+MF6? decompose into MF5 and (CF3)2NCH3.  相似文献   

3.
Bromosulfenyl(trihalogeno)phosphonium Salts Cl3?nBrnPSBr+AsF6? (n = 0 – 3) and Cl3PSBr+SbF6? — Oxidative Bromination of Thiophosphorylhalides The bromosulfenyl(trihalogeno)phosphonium salts Cl3?nBrnPSBr+AsF6? (n = 0 – 3) and Cl3PSBr+SbF6? are prepared by oxidative bromination of the corresponding thiophosphorylhalides with Br2/MF5 (M = As, Sb) and characterized by vibrational and NMR spectroscopy.  相似文献   

4.
Methyloxoniumhexafluorometallates – Synthesis, Spectroscopic Characterization and Crystal Structure of H3COH2+AsF6 Up to now the protonation of methanol as a hydrogen bridged dimethanolium ion [H(CH3OH)2]+ was observed by different X-ray crystal structure studies. Now the preparation of H3COH2+MF6 in super acid media HF/MF5 (M = As, Sb) is reported. The thermolabile and moisture sensitive salts are characterized by vibrational and NMR spectroscopy. H3COH2+AsF6 crystallizes in the monoclinic space group P21/m (No. 11) with a = 487.8(1), b = 714.0(2), c = 848.2(2) pm, β = 98.03°(2) with 2 formula units per unit cell.  相似文献   

5.
Preparation of Dichlornitronium-hexafluoroarsenate and -hexafluoroantimonate ONCl2+MF6?(M = As, Sb) The preparation of ONCl2+MF6? (M = As, Sb) by oxidative chlorination of CNCl with Cl2/AsF5 and Cl2/SbF5 is reported. Both salts are characterized by Raman Spectroscopy. The difficulties in evaluating a force field for the cation are discussed.  相似文献   

6.
Acetamide and thioacetamide react with the superacid solutions HF/MF5 (M = As, Sb) under formation of the corresponding salts [H3CC(OH)NH2]+MF6 and [H3CC(SH)NH2]+MF6 (M = As, Sb), respectively. The reaction of DF/AsF5 with acetamide and thioacetamide lead to the corresponding deuterated salts [H3CC(OD)ND2]+AsF6 and [H3CC(SD)ND2]+AsF6, respectively. The salts are characterized by vibrational and NMR spectroscopy, and in the case of [H3CC(OH)NH2]+AsF6 and [H3CC(SH)NH2]+AsF6 also by single‐crystal X‐ray analyses. The [H3CC(OH)NH2]+AsF6( 1 ) salt crystallizes in the triclinic space group P$\bar{1}$ with two formula units per unit cell, and the [H3CC(SH)NH2]+AsF6( 2 ) salt crystallizes in the monoclinic space group P21/c with four formula units per unit cell. In both crystal structures three‐dimensional networks are observed which are formed by intra‐ and intermolecular N–H ··· F and O–H ··· F or S–H ··· F hydrogen bonds, respectively. For the vibrational analyses, quantum chemically calculated spectra of the cations [H3CC(OH)NH2 · 3HF]+ and [H3CC(SH)NH2 · 2HF]+ are considered.  相似文献   

7.
On the Reactions of CH3OCl, CF3OCl, CF3OF, and CF3OH with the Superacid System HF/MF5 (M = As, Sb). Preparation and Characterization of CH3OCl(H)+MF6? and CF3OCl(H)+MF6? The preparation of the chlorine oxoniumsalts CH3OCl(H)+MF6? and CF3OCl(H)+MF6? by protonation of CH3OCl and CF3OCl in the superacid solution of HF/MF5 (M = As, Sb) is described. However CF3OF and CF3OH have not been protonated under the same conditions. In the case of CF3OH the formation of F2CO · MF5 is observed. The novel compounds are characterized by nmr- and vibrational spectroscopy.  相似文献   

8.
On the Crystal Structures of CH3PF2H+AsF6? and CH3PF2H+SbF6? and a simple Method for Preparation of CH3PF2 A simple method for preparation of CH3PF2 from CH3PCl2 is reported. The phosphonium salts CH3PF2H+MF6? are obtained by the reaction of CH3PCl2 with superacidic systems HF/MF5 (M = As, Sb). CH3PF2H+SbF6? crystallizes in the space group P1 with a = 548.4(4) pm, b = 695.5(8) pm, c = 960.2(9) pm, α = 94.68(5)°, β = 97.19(6)°, γ = 94.41(6)° and Z = 2. CH3PF2H+SbF6? crystallizes in P1 with a = 554.3(3), b = 724.2(4), c = 970.4(5), α = 94.73(4)°, β = 96.14(5)°, γ = 95.30(4)°.  相似文献   

9.
The Synthesis of the Dichloromethylene-halogenosulfenium Salts Cl2CSCl+ AsF6? and Cl2CSBr+ AsF6? The sulfenium salts Cl2CSCl+ AsF6? and Cl2CSBr+ AsF6? are synthesized by oxidative halogenation of thiophosgene, Cl2CS with X2/AsF5 (X = Cl, Br) at 195 K and are characterized by vibrational as well as NMR spectroscopy.  相似文献   

10.
Synthesis and Spectroscopic Characterization of the Cyanonitrilium Salts NCCNH+MF?6 and the N-Methyl-cyanonitrilium Salts NCCNCH3+MF6? (M = As, Sb) The cyanonitrilium salts NCCNH+MF?6 (M = As, Sb) are prepared by protonation of cyanogene (CN)2 in the superacid HF/MF5 at 195 K. The synthesis of the N-methyl-cyanonitrilium salts NCCNCH3+MF6? (M = As, Sb) is proceeded by methylation of cyanogene by CH3OSO+MF6? in SO2 also at low temperature. All salts are characterized by vibrational and NMR spectra.  相似文献   

11.
Synthesis of the Dichloromethyleneiminium Salts Cl2C?NClH+MF6? and Cl2C?NClCH3+ MF6? (M = As, Sb) and Crystal Structure of Dichloromethyleneiminium-hyxachloroantimonate Cl2C?NH2+SbCl6? The N-chloro-dichloromethyleneiminium salts Cl2C=NCIH+MF6? (M = As, Sb) are prepared by protonationof trichloromethyleneimine in the superacide system HF/MF5 at 195 K. The synthesis of the N-chloro-N-methyl-dichloromethyleneiminium salts Cl2C?NClCH3+MF6? (M = As, Sb) is proceeded by methylation of perchloromethylenimine by CH3OSO+MF6? in SO2 also at low temperature. All salts are characterized by vibrational and NMR spectra. The dichloromethyleneiminiumhexachloroantimonate crystallizes in the space group P21/c with a = 971.3(4)pm, b = 1134.0(4)pm, c = 2154.2(7)pm β = 102.04(3)° and Z = 8.  相似文献   

12.
Preparation of N-Methylhalidonitrilium Salts XCNCH3+MF6? (X = Cl, Br, I; M = As, Sb) and the N-Methyl-trifluoroacetonitrilium Salts CF3CNCH3+MF6? The N-methyl-halidonitrilium salts XCNCH3+MF6? (X = Cl, Br, I; M = As, Sb) are synthesized by methylation of cyanogen halides with CH3F/MF5 in SO2 at low temperatures. The N-methyl-trifluoroacetonitrilium salts CF3CNCH3+MF6? (M = As, Sb) are formed analogous with trifluoroacetonitrile. All salts are characterized by vibrational and NMR spectroscopy.  相似文献   

13.
About the Preparation of N-Chloro-N-Methylammonium Salts (CH3)nNCl4–n+MF6? (n = 1–3; M = As, Sb) and (CH3)2NClX+MF6? (X = F, Br) Simple one-step methods for the preparation of the methylated chloroammonium salts (CH3)nNCl4–n+MF6? (n = 1–3; M = As, Sb) and for (CH3)2NClX+MF6? (X = F, Br) are reported. Their vibrational and NMR-spectroscopical data are discussed in comparison.  相似文献   

14.
Preparation of CF3SClF+MF6? (M = As, Sb) and Crystal Structure of CF3SCl2+SbF6? CF3SClF+MF6? (M = As, Sb) is prepared by oxidative fluorination of CF3SCl with XeF+MF6?. The new salt is characterized by IR, Raman and NMR spectra in comparison with CF3SF2+MF6? and CF3SCl2+MF6?. In SO2 solution CF3SClF+SbF6? symmetrizises into CF3SF2+SbF6? and crystalline CF3SCl2+SbF6? with the monoclinic space group P21/c with a = 773.5(14) pm, b = 954.8(15) pm, c = 1242.0(18) pm, β = 100.24(8)°, Z = 4.  相似文献   

15.
A single crystal of Br3+AsF6? was isolated from a sample of BrF2+AsF6? which had been stored for 20 years. It was characterized by x-ray diffraction and Raman spectroscopy. It is shown that Br3+AsF6? (triclinic, a = 7.644(7) Å, b = 5.641(6) Å, c = 9.810(9) Å, α = 99.16(8)°, β = 86.61(6)°, γ = 100.11(7)°, space group P1 R(F) = 0.0608) is isomorphous with I3+AsF6?. The structure consists of discrete Br3+ and AsF6? ions with some cation-anion interaction causing distortion of the AsF6? octahedron. The Br3+ cation is symmetric with a bond distance of 2.270(5) Å and a bond angle of 102.5(2)°. The three fundamental vibrations of Br3+ were observed at 297 (ν3), 293 (ν1), and 124 cm?12). The Raman spectra of Cl3+AsF6? and I3+AsF6? were reinvestigated and ν3(B1) of I3+ was reassigned. General valence force fields are given for the series Cl3+, Br3+, and I3+. Reactions of excess Br2 with either BrF2+AsF6? or O2+AsF6? produce mixtures of Br3+AsF6? and Br5+AsF6?. Based on its Raman spectra, the Br5+ cation possesses a planar, centrosymmetric structure of C2h symmetry with three semi-ionically bound, collinear, central Br atoms and two more covalently, perpendicularly bound, terminal Br atoms.  相似文献   

16.
Gas Phase Structure of CF3NCl2 and Preparation of CF3NCl2F+MF6? (M = As, Sb) and CF2 = NCl2F+SbF6? The gas phase structure of CF3NCl2 is reported. The following skeletal parameters are derived (ra-values, error limits are 3σ values): N? C = 1.470(6) Å, N? Cl = 1.733(3) Å, ClNCl = 111.5(4)° and ClNC = 107.6(5)°. CF3NCl2F+MF6? is prepared by fluorination of CF3NCl2 with XeF+MF6?. The same educt CF3NCl2 reacts with XeF+SbF6? at ?40°C to CF2 = NClF+SbF6? under elimination of ClF.  相似文献   

17.
Preparation and Spectroscopic Characterization of the Fluorophosphonium Salts X2FPSCH3+MF6? (X = Br, Cl; M = As, Sb) and XF2PSCH3+SbF6? (X = Br, Cl, F) The preparation of the fluorophosphonium salts X2FPSCH3+MF6? (X = Br, Cl; M = As, Sb) and XF2PSCH3+SbF6? (X = Br, Cl, F) by methylation of the corresponding thiophosphorylhalides in the system CH3F/SO2/MF5 (M = As, Sb) is reported. The new salts are characterized by their vibrational and NMR spectra.  相似文献   

18.
Preparation of N-Methyl-N-chlornitryl Hexafluoro Metallates ON(Cl)CH3+MF6? (M = As, Sb) . The preparation of ON(Cl)CH3+MF6? (M = As, Sb) by methylation of ONCl with CH3OSO+MF6? (M = As, Sb) is reported. Both salts were unlimited stable at - 78°C. The nitryl cation which is isoelectronic with acetyl chloride was identified by vibrational spectroscopy as N-chloro-N-hydroxy-methaneiminium cation in the solid state.  相似文献   

19.
The Preparation of Methylthio(trihalogeno)phosphonium Salts ClnBr3?nPSCH3+MF6?(n = 0–3; M = As, Sb) and Hal3PSCH3+SbCl6?(Hal = Br, Cl) The methylthio(trihalogeno) phosphonium salts BrnCl3?nPSCH3+MF6? (n = 0–3; M = As, Sb) are prepared by methylation of the corresponding thiophosphorylhalides BrnCl3?nPS in the system SO2/CH3F/MF5. The hexachloroantimonates Hal3PSCH3+SbCl6?(Hal = Br, Cl) are synthesized by thiomethylation of PBr3 and PCl3 with CH3SCl/SbCl5. All salts are characterized by vibrational and NMR spectroscopy.  相似文献   

20.
Preparation of (C6F5)2SF+MF6? (M ? As, Sb) and Crystal Structure of (C6F5)2SF+SbF6? XeF+MF6? (M ? As, Sb) reacts with (C6F5)2S in HF to form (C6F5)2SF+MF6?. The deeply violet sulfonium salts can be kept without decomposition up to 24 h at room temperature. The hexafluoroantimonate salt crystallizes in the monoclinic space group P21/n with a = 1056.4(7) pm, b = 1446.3(10) pm, c = 1102.9(8) pm, β = 91.29(6)° und Z = 4. The SF-bond distance with 158.4(3) pm is of unusual length. Cations and anions are connected via interionic fluorine contacts to an infinite chain, in which cations and anions form to ABAB sequence along the chain.  相似文献   

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