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.     

Über die Darstellung der Dichlormethylen-halogensulfenium-Salze Cl2CSCl+ AsF6− und Cl2CSBr+ AsF6− [1]

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.     

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.     

Schwingungsspektroskopische Untersuchungen an Trimethylphosphonium-Kationen (CH3)3PX+ (X = H,D) und Kristallstrukturen von (CH3)3PD+SbCl6− und (CH3)3PCl+SbCl6−

Vibrational Spectra of Trimethylphosphonium Cations (CH₃)₃PX⁺ (X = H, D) and Crystal Structures of (CH₃)₃PD⁺SbCl₆^? and (CH₃)₃PCl⁺SbCl₆^? The trimethylphosphonium salts (CH₃)₃PX⁺SbCl₆^? (X = H, D) and (CH₃)₃PH⁺MF₆^? (M = As, Sb) are prepared and characterized by vibrational and NMR spectroscopy (¹H, ³¹P, ¹³C). In addition the crystal structures of (CH₃)₃PD⁺SbCl₆^? and (CH₃)₃PCl⁺SbCl₆^? are reported. (CH₃)₃PD⁺SbCl₆^? crystallizes in the orthorhombic space group Pnma with a = 1555(1) pm, b = 753.1(8) pm, c = 1166(1) pm Z = 4. (CH₃)₃PCl⁺SbCl₆^? crystallizes triclinic in the space group P1 with a = 704.6(4) pm, b = 729.5(3) pm, c = 1391.1(7) pm, α = 89.57(4)°, b? = 88.04(4)°, γ = 74.98(4)° and Z = 2.     

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.     

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 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 und Kristallstruktur der Pnictidoxide Na2Ti2As2O und Na2Ti2Sb2O

Preparation and Crystal Structure of the Pnictide Oxides Na₂Ti₂As₂O and Na₂Ti₂Sb₂O Na₂Ti₂As₂O and Na₂Ti₂Sb₂O were synthesized in form of very easily hydrolysed metallic-grey powders by reaction of Na₂O and TiAs resp. TiSb in sealed tantalum tubes under argon. The tetrahedral bodycentered crystallizing compounds from a modified anti-K₂NiF₄ structure type [1] (also called Eu₄As₂O-type [2,3]), space group I4/mmm (no. 139), with the lattice constants for Na₂Ti₂As₂O: a = 407.0(2) pm, c = 1528.8(4) pm and for Na₂Ti₂Sb₂O: a = 414.4(0) pm, c = 1656.1(1) pm. Magnetic measurements of powder samples of Na₂Ti₂Sb₂O show antiferromagnetic interaction within the Ti—O-layers. Superconductivity was not found by ac-shielding method down to 4 K.     

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.     

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 und Charakterisierung von Iodoplatinaten MexNH4–xPtI4 (x = 2 − 4), gemischtvalenten Octaiododiplatinaten(II,IV) mit Pt2I8-Baugruppen

Preparation and Characterization of Iodoplatinates Me_xNH_4–xPtI₄ (x = 2–4), Mixed Valence Octaiododiplatinates(II,IV) with Pt₂I₈ Groups Iodoplatinates APtI₄ (A = Me_xNH_4–x with x = 2–4) have been prepared by partial oxidation of the correspondent hexaiododiplatinates(II) A₂Pt₂I₆ with I₂ in methanolic solutions. X-ray structure analyses of the bronze-coloured needle-shaped crystals of the compounds showed rows of dinuclear anions Pt₂I₈^2?, built up by edgesharing planar PtI₄ groups with Pt^II und octahedral PtI₆ groups with Pt^IV. The different space requirement of the cations leads to the formation of three different structures. Within the anion stacks weak intermolecular Pt^IV? I …? Pt^II interactions are detectable by Raman spectroscopy.     

Über die Darstellung der Trimercaptosulfoniumsalze [S(SH)3]+AsF6− und [S(SH)3]+SbCl6−

Preparation of Trimercaptosulfonium Salts [S(SH)₃]⁺AsF₆^? and [S(SH)₃]⁺SbCl₆^? The preparation of the trimercaptosulfonium salts [S(SH)₃]⁺AsF₆^? and [S(SH)₃]⁺SbCl₆^? from SCl₃⁺ salts with excessive H₂S at 193 K is reported. The [S(SH)₃]⁺SbCl₆^? is transferred into [S(SCl)₃]⁺SbCl₆^? by reaction with Cl₂ at low temperatures. The new [S(SH)₃]⁺ cation is isoelectronic to P(PH₂)₃. In addition, its existence is supported by an ab-initio calculation. The results show a potential well for C_3v configuration with SH bonds bended towards the top of the pyramid for the isolated ion. Also the results of a force-field calculation are reported.     

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.     

Kristallstruktur,Schwingungsspektren und Normalkoordinatenanalyse von K2[IrCl5(NH3)]

Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of K₂[IrCl₅(NH₃)] The X-ray structure determination of K₂[IrCl₅(NH₃)] (orthorhombic, space group Pnma, a = 13.426(4), b = 10.015(2), c = 6.8717(7) Å, Z = 4) revealed the C_s point symmetry of the complex anion [IrCl₅(NH₃)]^2? (Ir? Cl = 2.337–2.365, Ir? N = 2.067(10); N? H = 0.73–0.79 Å). Using the molecular parameters the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(NH) = 5.88, f_d(IrN) = 2.66, f_d(IrCl) = 1.68 mdyn/Å.     

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 und Kristallstruktur des ionischen Tellurnitridchlorids [Te3N2Cl5(SbCl5)]+SbCl6−

Synthesis and Crystal Structure of the Ionic Tellurium Nitride Chloride[Te₃N₂Cl₅(SbCl₅)]⁺SbCl₆^? The title compound has been prepared by the reaction of Te₂NCl₅ with antimony pentachloride in CH₂Cl₂ suspension. It is characterized by IR spectroscopy and by a crystal structure determination. Space group P2₁/c, Z = 4, lattice dimensions at ?70°C: a = 1535.6, b = 1259.5, c = 1572.4 pm, β = 109.30°, R = 0.031. The compound forms an ionic pair with the central group of a (TeNCl)₂ molecule in which the tellurium atoms are linked by the nitrogen atoms to give a planar Te₂N₂ four-membered ring. One of the nitrogen atoms is coordinated by a TeCl₃⁺ unit, the other one by an antimony pentachloride molecule. According to the IR spectra a structure like [Te₂N₂Cl₂(TeCl₄)₂] is proposed for Te₂NCl₅.     

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 von Nonahalogenodiplatinaten(IV), [Pt2X9]−, X  Cl,Br Spektroskopische Charakterisierung,Normalkoordinatenanalyse und Kristallstruktur von (PPN)[Pt2Br9]

Preparation of the Nonahalogenodiplatinates(IV), [Pt₂X₉]^?, X ? Cl, Br Spectroscopic Characterization, Normal Coordinate Analysis, and Crystal Structure of (PPN)[Pt₂Br₉] On heating the tetrabutylammonium salts (TBA)₂[PtX₆], with trifluoroacetic acid the nonahalogenodiplatinates(IV) (TBA)[Pt₂X₉], with X ? Cl, Br are formed. The X-ray structure determination on (PPN)[Pt₂Br₉] (orthorhombic, space group Pca2, Z = 4) shows for the anions pairs of face-sharing octahedra with nearly D_3h symmetry. The mean terminal and bridging Pt? Br bond lengths are determined to be 2.42 and 2.52 Å, respectively. The electrostatic interaction of the Pt atoms results in the Pt? Pt distance of 3.23 Å and an elongation as it has been forecasted by the MO scheme for d⁶ systems. Using the structural data a normal coordinate analysis based on a general valence force field for [Pt₂Br₉]^? has been performed, revealing a good agreement of the calculated frequencies with the bands observed in the IR and Raman spectra. The stronger bonding of the terminal as compared to the bridging ligands is shown by the valence force constants, f_a(Br₁) = 1,55 > f_d(Br_b) = 0,93 mdyn/ Å.     

Darstellung,Kristallstruktur, Schwingungsspektren und Normalkoordinatenanalyse von [Co(NH3)6][Os(SCN)6]

Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of [Co(NH₃)₆][Os(SCN)₆] From the mixture of the linkage isomers [Os(NCS)_n(SCN)_6–n]^3–, n = 0–2, pure [Os(SCN)₆]^3– has been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X‐ray structure determination on a single crystal of [Co(NH₃)₆][Os(SCN)₆] (trigonal, space group R 3, a = 12.368(2), c = 11.830(2) Å, Z = 3) reveals that the thiocyanate ligands are exclusively S‐coordinated with the Os–S distance of 2.388 Å and the Os–S–C angle of 108.8°. The IR and Raman spectra of (n‐Bu₄N)₃[Os(SCN)₆] are assigned by normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constant f_d(OsS) is 1.42 mdyn/Å.