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.     

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.     

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.     

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.     

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 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.     

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.     

Darstellung von CF3SClF+MF6− (M = As,Sb) und Kristallstruktur von CF3SCl2+SbF6−

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.     

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 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.     

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.     

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 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.     

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^?.     

Dimethyl(methansulfinyl)sulfoniumhexafluorometallate (CH3)2SS(O)CH3+MF6− (M = As,Sb) und Kristallstruktur von Methansulfinylchlorid [1]

Dimethyl(methanesulfinyl)sulfonium Hexafluorometallates (CH₃)₂SS(O)CH₃⁺MF₆^? (M = As, Sb) and the Crystal Structure of Methanesulfinylchloride CH₃S(O)Cl [1] The preparation of dimethyl(methanesulfinyl)sulfoniumhexafluorometallates (CH₃)₂SS(O)CH₃⁺MF₆^? (M = As, Sb) and the spectroscopic characterization of the new thiosulfonium salts are described. Alternatively they can be obtained from methylmethanethiosulfinate by methylation. In addition the crystal structure of methanesulfinylchloride CH₃S(O)Cl at 113 K is reported. The compound crystallizes in the monoclinic space group P2₁/n with a = 528.2(1), b = 829.2(2), c = 880.9(2) pm, β = 90.48(2)° and Z = 4.     

Darstellung von Trifluormethylhalogen-Iodaten(I) des Typs (CH3)4N+CF3IX− (X = F,Cl, Br) und Trifluormethyltrifluormethoxyiodat(I) (CH3)4N+CF3IOCF3−

Preparation of Trifluormethylhalogen Iodate(I) Salts (CH₃)₄N⁺CF₃IX^? (X = F, Cl, Br) and Trifluormethyltrifluormethoxy Iodate(I) (CH₃)₄N⁺CF₃IOCF₃^? We describe the preparation of new trifluormethyliodate(I) salts CF₃IX^? (X = F, Cl, Br, OCF₃). (CH₃)₄N⁺CF₃ICl^? and (CH₃)₄N⁺CF₃IBr^? are obtained via addition of CF₃I with the corresponded tetramethylammonium halogenide. (CH₃)₄N⁺CF₃IOCF₃^? is synthesized by comproportionation of (CH₃)₄N⁺CF₃ICl^? with CF₃OCl under formation of Cl₂ at ?78°C. (CH₃)₄N⁺CF₃IF^? is formed either, through thermolysis of (CH₃)₄N⁺ CF₃IOCF₃^? under separation of COF₂, or reaction of CF₃I with (CH₃)₄N⁺ OCF₃^?. The thermolabile compounds have been characterized by i.r., Raman, ¹⁹F-, ¹³C 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)°.     

Dimethylhydroxyoxosulfonium(VI) Hexafluoridometallates, [(CH3)2SO(OX)]+[MF6]–(X = H,D; M = As,Sb)

Dimethylsulfone reacts in the binary superacidic systems XF/MF₅ (X = H, D; M = As, Sb) under the formation of the corresponding salts of the type [(CH₃)₂SO(OX)]⁺[MF₆]^–. The salts are characterized by low temperature vibrational spectroscopy. In case of [(CH₃)₂SO(OH)]⁺[SbF₆]^– a single‐crystal X‐ray structure analysis is reported. The salt crystallizes in the orthorhombic space group Pbca with eight formula units per unit cell [a = 10.3281(3) Å, b = 12.2111(4) Å, c = 13.9593(4) Å]. The experimental results are discussed together with quantum chemical calculations on the PBE1PBE/6‐311G++(3pd,3df) level of theory.     

Magnesiumphthalocyanine: Darstellung und Eigenschaften von Halogenophthalocyaninatomagnesat, [Mg(X)Pc2−]− (X = F,Cl, Br); Kristallstruktur von Bis(triphenylphosphin)iminiumchloro(phthalocyaninato)magnesat-Aceton-Solvat

Magnesium Phthalocyanines: Synthesis and Properties of Halophthalocyaninatomagnesate, [Mg(X)Pc^2?]^? (X = F, Cl, Br); Crystal Structure of Bis(triphenylphosphine)iminiumchloro-(phthalocyaninato)magnesate Acetone Solvate Magnesium phthalocyanine reacts with excess tetra(n-butyl)ammonium- or bis(triphenylphosphine)iminiumhalide ((ⁿBu₄N)X or (PNP)X; X = F, Cl, Br) yielding halophthalocyaninatomagnesate ([Mg(X)Pc^2?]^?; X = F, Cl, Br), which crystallizes in part as a scarcely soluble (ⁿBu₄N) or (PNP) complex-salt. Single-crystal X-ray diffraction analysis of ^b(PNP)[Mg(Cl)Pc^2?] · CH₃COCH₃ reveals that the Mg atom has a tetragonal pyramidal coordination geometry with the Mg atom displaced out of the center (Ct) of the inner nitrogen atoms (N_iso) of the nonplanar Pc ligand toward the Cl atom (d(Mg? Ct) = 0.572(3) Å; d(Mg? Cl) = 2.367(2) Å). The average Mg? N_iso distance is 2.058 Å. Pairs of partially overlapping anions are present. The cation adopts a bent conformation (^b(PNP)⁺: d(P1? N(K)) = 1.568(3) Å; d(P2? N(K)) = 1.587(3) Å; ?(P1? N(K)? P2) = 141.3(2)°). Electrochemical and spectroscopic properties are discussed.