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.     

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.     

Preparation of Pseudohalidoheptasulfur(+1) Hexafluorometallates S7X+MF−6 (X = CN,OCN, SeCN; M = As,Sb)

The preparation and spectroscopic characterization of S₇X⁺MF^?₆ (X = CN, OCN, SCN, SeCN; M = As, Sb) is reported. The new compounds are formed in analogy to the preparation of halidocycloheptrasulfur(+1) cations from S²⁺₈(MF^?₆)₂ and alkali pseudohalides in So₂ as solvent. Their thermal stabilities decrease with the increasing Pearson hardness of the pseudohalide ligands.     

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 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.     

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.     

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.     

Metallorganische Lewis-Säuren. XLII. Carbonyl- und Nitrosyl-Komplexe von Mangan und Rhenium mit schwach koordinierten Anionen (Ph3P)2(ON)2MnX, (Ph3P)n(OC)5–nMX (M = Mn,Re; n = 1, 2; X = FBF3, OSO2CF3, OSO2F,OCORf)

Organometallic Lewis Acids. XLII. Carbonyl- and Nitrosyl Complexes of Manganese and Rhenium of Weakly Coordinated Anions (Ph₃P)₂(ON)₂MnX, (Ph₃P)_n(OC)_5–nMX (M = Mn, Re; n = 1, 2; X = FBF₃, OSO₂CF₃, OSO₂F, OCOR_f) The complexes (Ph₃P)₂(ON)₂MnX (X = FBF₃, OSO₂CF₃, OSO₂F, OCOCF₃, OCOC₃F₇) and (Ph₃P)_n(OC)_5–nMX (M = Mn, Re; n = 1, 2; X = FBF₃, OSO₂CF₃) have been obtained by reaction of (Ph₃P)₂(ON)₂MnH and (Ph₃P)_n(OC)_5–nMeMe with the corresponding acids HX or from (Ph₃P)_n(OC)_5–nReBr (n = 1, 2) with silver salts AgX, respectively. The compounds have been characterized by their IR and partially by ¹⁹F-NMR data. An efficient method for the preparation of the hydride (Ph₃P)₂(ON)₂MnH is reported.     

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.     

Über die Darstellung der Pnikogenoniumsalze AsH4+SbF6−, AsH4+AsF6−, SbH4+SbF6−

On the Preparation of Pnikogenonium Salts AsH₄⁺SbF₆^?, AsH₄⁺AsF₆^?, SbH₄⁺SbF₆^? The preparation of the pnikogenonium salts AsH₄⁺SbF₆^?, AsH₄⁺AsF₆^? and SbH₄⁺SbF₆^? by protonation from the hydrides AsH₃, SbH₃ in superacidic systems HF/SbF₅ and HF/AsF₅, resp. is reported. The salts are characterized by vibrational and mass spectra. A general valence force field is calculated. The following onium ions are know as hexafluoroantimonate:      

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 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.     

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.     

Darstellung und spektroskopische Charakterisierung von Di(acido)phthalocyaninatorhodaten(III)

Preparation and Spectroscopical Characterization of Di(acido)phthalocyaninatorhodates(III) Triethylendiaminorhodiumiodide reacts quickly and completely with boiling phthalodinitrile precipitating ?rhodiumphthalocyanine”?, which is purified and dissolved in alkaline media as di(hydroxo)phthalocyaninatorhodate(III). Acidification in the presence of halides or pseudohalides yields less soluble acidophthalocyaninatorhodium reacting with tetra-n-butyl-ammonium(pseudo)halide to give (blue)green tetra-n-butyl-ammoniumdi(acido)phthalocyaninatorhodate(III), (ⁿBu₄N)[Rh(X)₂Pc^2?] (X = Cl, Br, I, N₃, CN, NCO, SCN, SeCN). The asym. Rh? X-stretching vibration (v_as(RhX)) is observed in the f.i.r. at 290 (X = Cl), 233 (Br), 205 (I), 366 (N₃), 347 (CN), 351 (NCO), 257 (SCN) and 214 cm^?1 (SeCN). v_s(RhI) is the only sym. Rh? X-stretching vibration excited at 131 cm^?1 in the Raman spectrum. The m.i.r. and resonance Raman spectra are typical for hexacoordinated phthalocyaninatometalates(III). The influence of the axial ligands is very small. The frequency of the stretching vibrations of the pseudohalo-ligands are as expected (in the case of the ambident ligands the bonding atom is named first): v_as(NN) at 2006 and v_s(NN) at 1270 cm^?1 (N₃); v_as(CN) at 2126 (CN), 2153 (NCO), 2110 (SCN) and 2116 cm^?1 (SeCN). The characteristic π–π*-transitions of the Pc^2?-ligand dominate the UV-vis spectra. The splitting of the Q and N region is discussed and the weak absorbance at ca. 22 kK is assigned to a n–π*-transition.     

Darstellung und spektroskopische Eigenschaften von Nitridophthalocyaninatorhenium(V)

Preparation and Spectroscopical Properties of Nitridophthalocyaninatorhenium(V) Nitridophthalocyaninatorhenium(V) ([ReNPc^2?]) is prepared by the reaction of dirheniumheptoxide with ammoniumiodide in molten 1,2-dicyano-benzene. The diamagnetic complex is chemically und thermically extremely stable. In the Uv-vis spectra the typical π-π*-transitions of the Pc^2? ligand are observed. Extra bands in the solid state spectrum are due to strong excitonic coupling of ca. 2.8 kK. In the resonance Raman spectra the intensity of the Re≡N stretching vibration (v(Re≡N)) at 969 cm^?1 is selectively enhanced by laser excitations above 19.0 kK. v(Re≡N) is a dominant m.i.r. absorption at 976 cm^?1.     

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)°.     

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 μ-Schwefeldisulfoniumsalzen [(CH3)2S?Sx?S(CH3)2]2+2A− (x = 1–3, A− = AsF6−, SbF6−, SbCl6−). Über die Analogie im Reaktionsverhalten zwischen Sulfanen und Sulfoniumsalzen

Preparation of μ-Sulfurdisulfonium Salts [(CH₃)₂S? S_x? S(CH₃)₂]²⁺2A^? (x = 1–3, A^? = AsF₆^?, SbF₆^?, SbCl₆^?). On the Analogy of the Reactivity of Sulfanes and Sulfonium Salts The preparation of the μ-sulfurdisulfonium salts [(CH₃)₂S? S_x? S(CH₃)₂]²⁺(A^?)₂ with x = 1–3 and A^? = AsF₆^?, SbF₆^?, SbCl₆^? is reported. The salts are formed by reaction of (CH₃)₂SH⁺A^? and (CH₃)₂SSH⁺A^? with SCl₂ and S₂Cl₂, resp. They are characterized by vibrational spectroscopic measurements. [(CH₃)₂S? S₂? S(CH₃)₂]²⁺(SbF₆^?)₂ crystallizes in the space group C2/c with a = 1 884.5(7) pm, b = 1 302.8(5) pm, c = 1 477.2(5) pm, β = 98.62(3)° und Z = 8.     

Darstellung,Eigenschaften und elektronische Raman-Spektren von Bis(chloro)phthalocyaninatoferrat(III), -ruthenat(III) und -osmat(III)

Preparation, Properties and Electronic Raman Spectra of Bis(chloro)-phthalocyaninatoferrate(III), -ruthenate(III) and -osmate(III) Bis(chloro)phthalocyaninatometalates of Fe^III, Ru^III and Os^III [MCl₂Pc(2-)]^?, with an electronic low spin ground state are formed by the reaction of [FeClPc(2-)] resp. H[MX₂Pc(2?)] (M = Ru, Os; X = Cl, I) with excess chloride in weakly coordinating solvents (DMF, THF) and are isolated as (n-Bu₄N) salts. The asym. M? Cl stretch (ν_as(MCl)) is observed in the f.i.r. at 288 cm^?1 (Fe), 295 cm^?1 (Ru), 298 cm^?1 (Os), ν_as(MN) at 330 cm^?1 (Fe), 327 cm^?1 (Ru), and 317 cm^?1 (Os); only ν_s(OsCl) at 311 cm^?1 is resonance Raman (r.r.) enhanced with blue excitation. The m.i.r. and FT-Raman spectra are typical for hexacoordinated phthalocyanines of tervalent metal ions. The UV-vis spectra show besides the characteristic π-π* transitions (B, Q, N, L band) of the Pc ligand a number of extra bands at 12–15 kK and 18–24 kK due to trip-doublet and (Pc→M)CT transitions. The effect of metal substitution is discussed. The r.r. spectra obtained by excitation between the B and Q band (λ₀ = 476.5 nm) are dominated by the intraconfigurational transition Γ₇ Γ ₈ arrising from the spin-orbit splitting of the electronic ground state for Fe^III at 536 cm^?1, for Ru^III at 961 cm^?1 and Os^III at 3 028 cm^?1. Thus the spin-orbit coupling constant increases very greatly down the iron group: Fe^III (357 cm^?1)< Ru^III (641 cm^?1)< Os^III (2 019 cm^?1). The Γ₇ Γ ₈-transition is followed by a very pronounced vibrational finestructure being composed in the r.r. spectra by the coupling with ν_s(MCl), δ(MClN) and the most intense fundamental vibrations of the Pc ligand. In absorption only vibronically induced transitions are observed for the Ru and Os complex at 1 700-2800 rsp. 3100-5800 em^?1 instead of the 0-0 phonon transitions. The most intense lines are attributed to combinations of the intense odd vibrational mo-des at ≈ 740 and 1120 cm^?1 with ν₅(MCI), δ(MClN).