The reaction of XeF+MF6− (M = As,Sb) with sulfuranes; preparation of CF3(O)F2+SbF6− and (CF3)2SOXeF+SbF6−

CF₃S(O)F, (CF₃)₂SO, CF₃SF₃, (CF₃)₂SF₂, and SF₄ react in different manner with XeF⁺MF₆^? (M?As, Sb). An oxidative fluorination is observed by CF₃S(O)F forming the persulfonium salt CF₃S(O)F₂⁺SbF₆^?, whereas by (CF₃)₂SO a simple addition product containing xenon can be isolated in form of the sulfonium salt (CF₃)₂SOXeF⁺SbF₆^?. On the contrary, the Lewis-acidic character of the XeF⁺-cation predominates against (CF₃)_nSF_4?n (n = 0 ? 2) leading to the corresponding fluorosulfonium salts (CF₃)_nSF_3?n ⁺MF₆^? (M?As, Sb) and XeF₂.     

Über die Gasphasenstruktur von CF3NCl2 und die Darstellung von CF3NCl2F+MF6− (M = As,Sb) und CF2 = NClF+SbF6−

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 (r_a-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.     

Synthese von (C6F5)2SF+MF6− (M  As,Sb) und Kristallstruktur von (C6F5)2SF+SbF6− [1]

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.     

Darstellung und spektroskopische Charakterisierung der Persulfoniumsalze (CH3)(CF3)SF3+SbF6− und (CH3)(CF3)2SF2+SbF6− und Kristallstruktur von CF3SF2+SbF6−

Preparation and Spectroscopic Characterization of the Persulfonium Salts (CH₃)(CF₃)SF₃⁺SbF₆^? and (CH₃)(CF₃)₂SF₂⁺SbF₆^? and Crystal Structure of CF₃SF₂⁺SbF₆^? [1] . The preparation of the persulfonium salts (CH₃)(CF₃)SF₃⁺SbF₆^? and (CH₃)(CF₃)₂SF₂⁺SbF₆^? by methylation of the sulfuranes CF₃SF₃ and (CF₃)₂SF₂ with CH₃OSO⁺SbF₆^? in liquid SO₂ is reported. The thermolabile compounds are characterized by IR, Raman, ¹H, ¹³C, and ¹⁹F NMR spectroscopy. CF₃SF₂⁺SbF₆^? crystallizes in the space group C2/c with a=16.889(8) Å, b=7.261(4) Å, c=13.416(7) Å, β=91.08° with 8 formula units per unit cell at 167 K. Cations and anions are connected via short SF contacts forming a Ψ-octahedral surrounding of the central S atom which is in close analogy to the already known CF₃SF₂⁺AsF₆^?.     

Darstellung der Iminiumsalze CF3?NXCF2+MF6− (X = CH3, F und M = As,Sb) und CF3?NCl = CF2+ AsF6−

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.     

Die Darstellung der N-Methyl-halogennitrilium-Salze XCNCH3+MF6− (X = Cl,Br, I; M = As,Sb) und der N-Methyl-trifluoracetonitrilium-Salze CF3CNCH3+MG6−

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.     

Über die Kristallstrukturen von CH3PF2H+AsF6− und CH3PF2H+SbF6− und eine einfache Darstellung von CH3PF2

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)°.     

über die Reaktionen von CH3OCl,CF3OCl,CF3OF und CF3OH mit dem supersauren System HF/MF5 (M = As,Sb) Darstellung und Charakterisierung von CH3OCl(H)+MF6− und CF3OCl(H)+MF6−

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.     

Darstellung der Dichlormethyleniminium-Salze Cl2CNClH+ MF6− und Cl2CNClCH3+ MF6− (M = As,Sb) und Kristallstruktur von Dichlormethyleniminiumhexachloroantimonat Cl2CNH2+SbCl6−

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.     

Darstellung der Halogennitrilium-Salze XCNH+MF6− (X = Cl,Br, I; M = As,Sb) und der Trifluoracetonitrilium-Salze CF3CNH+MF6−

Preparation of the Halogenonitrilium Salts XCNH⁺MF₆⁻ (X = CI, Br, I; M = As, Sb) and the Trifluoroacetonitrilium Salts CF₃CNH⁺MF₆⁻ The halogenonitrilium salts XCNH⁺MF₆⁻ (X = CI, Br, I; M = As, Sb) are synthesized by protonation of cyanogen halides in the superacide system HF/MF₅ at low temperature. The synthesis of trifluoroacetonitrilium salts CF₃CNH⁺MF₆⁻ (M = As, Sb) is proceeded analogous with trifluoroacetonitrile. All salts are characterized by vibrational and NMR spectroscopy.     

Bromsulfenyl(trihalogen)phosphonium-Salze Cl3−nBrnPSBr+AsF6− (n = 0 – 3) und Cl3PSBr+SbF6− — Oxidative Bromierung von Thiophosphorylhalogeniden

Bromosulfenyl(trihalogeno)phosphonium Salts Cl_3?nBr_nPSBr⁺AsF₆^? (n = 0 – 3) and Cl₃PSBr⁺SbF₆^? — Oxidative Bromination of Thiophosphorylhalides The bromosulfenyl(trihalogeno)phosphonium salts Cl_3?nBr_nPSBr⁺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.     

Darstellung von Dichlornitronium-hexafluoroarsenat und -hexafluoroantimonat ONCl2+MF6−(M = As,Sb)

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.     

Bis(trifluoromethyl)fluorsulfonium(IV)-metallate(V) [1] (CF3)2SF+MF6- (M = As,Sb)

The preparation of (CF₃)₂SF⁺MF₆^- (M = As, Sb) is reported. New salts have been synthesized from the reaction of (CF₃)₂SF₂ with strong Lewis acids and CF₃SCF₃ with XeF⁺MF₆^- (M = As, Sb). They are characterised by Raman- and NMR - spectroscopy.     

Darstellung und spektroskopische Charakterisierung der Cyannitrilium-Salze NCCNH+MF6− und der N-Methyl-cyannitrillium-Salze NCCNCH3+MF6− (M = As,Sb)

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.     

Darstellung und spektroskopische Charakterisierung der Fluorphosphonium-Salze X2FPSCH3+MF6− (X = Br,Cl; M = As,Sb) und XF2PSCH3+SbF6− (X = Br,Cl, F)

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.     

Darstellung von N-Methyl-N-chlornitryl-hexafluorometallaten ON(Cl)CH3+MF6− (M = As,Sb)

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.     

Über die oxidative Fluorierung von (CF3)(R) (R = CF3, Cl) und die Kristallstruktur von (CF3)(Cl)F+ AsF6−

Oxidative Fluorination of (CF₃)(R) (R = CF₃, Cl) and the Crystal Structure of (CF₃)(Cl) F⁺ AsF₆^? Oxidative fluorination of (CF₃)(R) (R = CF₃, Cl) with XeF⁺MF₆^? (M = As, Sb) in anhydrous HF results in formation of monofluorsulfonium hexafluorometalates. The salts are characterized by vibrational, NMR, and mass spectra. (CF₃)(Cl)F⁺ AsF₆^? crystallizes in the monoclinic space group P2₁/c with a = 9.955(10) Å, b = 11.050(5) Å, c = 12.733(15) Å, β = 97.77(5)°, and Z = 4.     

Dihydroxycarbeniumhexafluorometallate – Synthese,spektroskopische Charakterisierung sowie Kristallstruktur von HC(OH)2+AsF6−

Dihydroxycarbeniumhexafluorometallates – Synthesis, Spectroscopic Characterization, and Crystal Structure of HC(OH)₂⁺AsF₆^? The preparation of HC(OH)₂⁺ MF₆^? (M = As, Sb) by protonation of HCOOH in the superacid systems HF/MF₅ is reported. The very hydrolysable and thermolabile salts are characterized by vibrational and NMR spectroscopic methods. Under inert conditions they are stable at ?40°C for some weeks. HC(OH)₂⁺AsF₆^? crystallizes in the orthorhombic space group Pbca (No. 61) with a = 965.8(1), b = 1582.20(16), c = 766.40(8) pm with eight formula units per unit cell.     

Über die Darstellung der N-Chlor-N-Methylammoniumsalze (CH3)nNCl4–n+MF6− (n = 1–3; M = As,Sb) und (CH3)2NCIX+MF6− (X = F,Br)

About the Preparation of N-Chloro-N-Methylammonium Salts (CH₃)_nNCl_4–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)_nNCl_4–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.     

Die Darstellung der Methylthio(trihalogen)phosphonium-Salze ClnBr3−nPSCH3+MF6−(n = 0–3; M = As,Sb) und Hal3PSCH3+SbCl6−(Hal = Br,Cl)

The Preparation of Methylthio(trihalogeno)phosphonium Salts Cl_nBr_3?nPSCH₃⁺MF₆^?(n = 0–3; M = As, Sb) and Hal₃PSCH₃⁺SbCl₆^?(Hal = Br, Cl) The methylthio(trihalogeno) phosphonium salts Br_nCl_3?nPSCH₃⁺MF₆^? (n = 0–3; M = As, Sb) are prepared by methylation of the corresponding thiophosphorylhalides Br_nCl_3?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.