Hydroxonium-hexachloroantimonate(V)

Hydroxonium Hexachloroantimonates(V) The hydroxonium hexachloroantimonates(V) H₅O₂⊕SbCl₆? (I), H₇O₃⊕SbCl₆? (III), H₉O₄⊕SbCl₆? (V) as well as the deuterated compounds D₅O₂⊕SbCl₆? (II), D₇O₃⊕SbCl₆? (IV) and D₉O₄⊕SbCl₆? (VI) were prepared by reaction of hydrogen chloride resp. deuterium chloride with water addition compounds of antimony(V) chloride. The i.r. spectra are discussed.     

Reaktionsprodukte aus Chlormethoxiphosphinen und Antimon(V)-chlorid. Schwingungsspektren der 1:1 Addukte aus Methoxiphosphorylverbindungen und Antimon(V)-chlorid

Reaction Products of Chloromethoxiphosphines and Antimony (V) Chloride. Vibrational Spectra of the 1:1-adducts of Methoxiphosphoryl Compounds and Antimony (V) Chloride Chloromethoxiphosphines react with antimony(V) chloride in a redox process to yield the chloromethoxiphospllonium hexachloroantimonates(V) (CH₃O)₃PCl₂⁺SbCl₆^? (II) and CH₃OPCl₃⁺SbCl₆^? (III). II, III, (CH₃O)₃PCl⁺SbCl₆^?(1) and (CH₃O)₄P⁺SbCl₆^? eliminate easily methyl chloride and give the addition compounds OP(OCH₃)₃·SbCl₅(IV), OPCl(OCH₃)₂ · SbCl₅ (V), OPCl₂(OCH₃)·SbCl₅ (VI) and OPCl₃·SbCl₅ (VII). The vibrational spectra of IV, V nnd VI are discussed.     

Über die Reaktion von Trimethylamin mit Antimon(V)-chlorid

Inhaltsübersicht. Trimethylamin und Antimon(V)-chlorid bilden keinen Dornor-Acceptor Komplex. In Abhängigkeit vom Molverhältnis reagieren die Komponenten zu (CH₃)₃NCl⁺SbCl₆^– (I) bzw. zu (CH₃)₃NH+X^– und (CH₃)₂N=CH₃⁺X^– (X^– = SbCl₆^–, SbCI₄^–, Sb₃CI₁₄^3– und CI^–). I kann in (CH₃)₃NH⁺SbCl₆^– und (CH₃)₂N=CH₂+SbCl₆^– zerfallen. The Reaction of Trimethylamine with Antimony (V) Chloride Abstract. Trimethylamine and antimony(V) chloride forms no donor-acceptor-complex. In dependence of the molar ratio the compounds reacts to (CH₃)₃NCl⁺SbCl₆^– (I) resp. to (CH₃)₃NH+X^– and (CH₃)₂N=CH₃⁺X^– (X^– = SbCl₆^–, SbCI₄^–, Sb₃CI₁₄^3– and CI^–). I can decompose into (CH₃)₃NH⁺SbCl₆^– and (CH₃)₂N=CH₂+SbCl₆^–.     

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.     

Über die Darstellung von Dimethyl(mercapto)sulfonium-hexa-chloroantimonat [(CH3)2SSH]+SbCl6−

Preparation of Dimethyl(mercapto)sulfonium-hexachloroantimonate [(CH₃)₂SSH]⁺SbCl₆^? The preparation of [(CH₃)₂SSH]⁺SbCl₆^? from [(Ch₃)₂SCl]⁺SbCl₆^? and H₂S at 223 K is reported. This salt is stable below 243 K and is characterized by vibrational spectroscopy.     

Untersuchungen über das Reaktionsverhalten von Antimonpentachlorid. III [1]. Zur Reaktion von Antimon (V)-chlorid mit Methylisocyanat

Studies on the Reactivity of Antimony Pentachloride. III. The Reaction of Antimony(V) Chloride and Methylisocyanate Methylisocyanate CH₃NCO reacts with SbCl₅ in boiling CCl₄ by an insertion-reaction to a product of the formula C₅H₆Cl₉N₂O₂Sb I, which has the chlorformamidinium-structure (Cl? C(O)? N(CH₃)? CCl? N(CH₃)? C(O)? Cl)⊕SbCl₆?. Hydrolysis of I yields the heterocycle C₅H₆N₂O₄ II. The reaction with methanol gives (CH₃? NH? CCl? NH? CH₃)⊕SbCl₆? III and (CH₃? NH? CCl? N(CH₃)? C(O)? OCH₃)⊕SbCl₆? IV. The i.r. and Raman spectra of the compounds I, III and IV are discussed.     

dh-μ-Carboxilato-e-μ-hydroxo-f-μ-oxo-bis[trichloroantimone(V)] Struktur und spektroskopsiche Untersuchungen

dh-μ-Carboxilato-e-μ-hydroxo-f-μ-oxo-bis[trichloroantimonies(V)] Structure and Spectroscopic Investigations The title compounds can be prepared by reaction of SbCl₅ · H₂O and RCOOH (R ? CF₃, CCl₃, CHCl₂, CH₂Cl, CH₃, CH₃CH₂, (CH₃)₂CH, H) or by reaction of H₅O₂⁺SbCl₆^? and RCO₂SbCl₄ in good yields. ¹H-NMR investigations proove that there is a rapid exchange between the components in the reaction mixture. The vibrational spectra are discussed in view of the CO₂ vibrations and hydrogen bonding. The crystal and molecular structure of dh-μ-Trichloroacetato-e-μ-hydroxo-f-μ-oxo-bis[trichloroantimony(V)] is determined by X-ray analysis.     

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.     

Kraftkonstanten von Verbindungen des Typs (CH3)3ElCl+X− (El = N,P, As,Sb; X− = SbCl6−)

Force Constants of Compounds of the Type (CH₃)₃ElCl⁺X^?(El = N, P, As, Sb; X^? = SbCl₆^?) For the cations (CH₃)₃NCl⁺ ( 1 ), (CH₃)₃PCl⁺ ( 2 ), (CH₃)₃AsCl⁺ ( 3 ), and (CH₃)₃SbCl⁺ ( 4 ) a normal coordinate analysis using a general valence force field is performed by the method of Fadini. The force constants are discussed. Calculations of the potential energy distribution show, that the skeletal vibrations in 4 are all characteristic vibrations, but there is a strong coupling of vibrations in 1 .     

Addukte aus Phosphorylverbindungen und SbCl5 Darstellung und IR-Spektren der 1:1-Addukte aus Chlordimethylamino- bzw. Chlordimethylamino-methoxi-phosphorylverbindungen und Antimon(V)-chlorid

Adducts of Phosphoryl Compounds and SbCl₅ Preparation and IR Spectra of 1:1 Addition Compounds from Chlorodimethylamino- resp. Chlorodimethylaminomethoxiphosphoryl Compounds and Antimony(V) Chloride The addition compounds (CH₃O)₂[(CH₃)₂N]PO · SbCl₅ ( II ), (CH₃O)[(CH₃)₂N]₂PO · SbCl₅ ( III ), [(CH₃)₂N]₃PO · SbCl₅ ( IV ), Cl₂[(CH₃)₂N]PO · SbCl₅ ( VI ), Cl[(CH₃)₂N]₂PO · SbCl₅ ( VII ), and Cl(CH₃O)[(CH₃)₂N]PO · SbCl₅ ( VIII ) are prepared by reaction of the phosphoryl compounds with antimony(V) chloride. The influence of the Lewis acid to the bonds of the phosphoryl compounds is discussed. The ³¹P-n.m.r. data of the adducts are communicated and compared with those of the free phosphoryl compounds.     

l-Hydroxo/Alkoxo-l-oxo-l-sulfonato-jO:jO'-bis[trichloroantimon(V)]Verbindungen. Zweikernige Antimon(V)-Komplexe mit Sulfonatgruppen als überbrückenden Liganden

l-Hydroxo/alkoxo-l-oxo-l-sulfonato-jO:jO'-bis[trichloroantimony(V)] Compounds. Binuclear Antimony(V) Complexes with Sulfonate Groups as bridging Ligands Sulfonic acids react with antimony(V) chloride and water and water/alcohol resp. dependent of the molar ratios yielding Cl₃SbO(OH)(O₂S(O)CH₃)SbCl₃ ( 1 ), Cl₃SbO(OH)· (O₂S(O)CF₃)SbCl₃ ( 3 ) the monohydrate Cl₃SbO(OH)· (O₂S(O)CH₃)SbCl₃·H₂O ( 2 ) and the compounds Cl₃SbO(OR')(O₂S(O)CF₃)SbCl₃ ( 4 : R'=CH₃; 5 : R'=C₂H₅) and Cl₃SbO(OCH₃)(O₂S(O)C₂H₅)SbCl₃ ( 6 ) resp. The crystal and molecular structures of 1 to 3 , 5 and 6 are determined. 1 and 3 are associated by hydrogen bonds to dimers and crystallize monoclinic ( 1 : P2₁/c; 3 : P2₁/n). 2 is a hydroxonium salt H₃O⁺[Cl₃SbO₂(O₂S(O)CH₃)SbCl₃]^– with strong hydrogen bonds between cations and anions and crystallizes triclinic (P1). 5 and 6 crystallize monoclinic ( 5 : P2₁/m; 6 : P2₁/c). In 1 and 3 to 6 there is an intramolecular reorientation or an intermolecular exchange of protons and R' groups in solution. The NMR spectra are discussed.     

Phosphaniminato-Komplexe des Antimons. Die Kristallstrukturen von [Sb2Cl5(NPMe3)2][SbCl6] · CH3CN und [SbCl(NPPh3)]2[SbCl6]2 · 6 CH3CN

Phosphorane Iminato Complexes of Antimony. The Crystal Structures of [Sb₂Cl₅(NPMe₃)₂][SbCl₆] · CH₃CN and [SbCl(NPPh₃)]₂[SbCl₆]₂ · 6 CH₃CN The title compounds are formed by reaction of antimony pentachloride in acetonitrile solution with the phosphorane iminato complexes SbCl₂(NPMe₃) and SbCl₂(NPPh₃), respectively, which themselves are synthesized by reaction of antimony trichloride with Me₃SiNPR₃ (R = Me, Ph). The complexionic compounds are characterized by ¹²¹Sb Mössbauer spectroscopy and by crystal structure determinations. [Sb₂Cl₅(NPMe₃)₂][SbCl₆] · CH₃CN: Space group P4₁, Z = 4, 3 698 observed unique reflections, R = 0.022. Lattice dimensions at ?60°C: a = b = 1 056.0(1), c = 2 709.6(2) pm. The structure consists of SbCl₆^? ions and cations [Sb₂Cl₅(NPMe₃)₂(CH₃CN)]⁺, in which one Sb^III atom and one Sb^V atom are bridged by the N atoms of the phosphorane iminato ligands. [SbCl(NPPh₃)]₂[SbCl₆]₂ · 6 CH₃CN: Space group P1 , Z = 2, 5 958 observed unique reflections, R = 0.033. Lattice dimensions at ?60°C: a = 989.4(11), b = 1 273(1), c = 1 396(1) pm, α = 78.33(7), β = 77.27(8)°, γ = 86.62(8)°. The structure consists of SbCl₆^? ions and centrosymmetric cations [SbCl(NPPh₃)(CH₃CN)₂]₂²⁺, in which the antimony atoms are bridged by the N atoms of the phosphorane iminato ligands.     

Schwingungs- und kernresonanzspektroskopische Untersuchungen am System Antimon(V)-chlorid/Methanol

Investigations of the System Antimony (V) Chloride/Methanol by Vibrational and N.M.R. Spectroscopy The 1 : 1 addition compound I of antimony(V) chloride and methanol reacts with further alcohol. In products with two resp. three methanol molecules these are bonded to I by H bridges (SbCl₅ · n CH₃OH; n = 1–3). More than three methanols yield to ionic products (H⁺(CH₃OH)_nSbCl₅OCH₃^?; n > 3). This can be demonstrated by spectroscopic methods. The vibrational and ¹H-n.m.r. spectra are assigned arid discussed.     

Beiträge zur Chemie der Schwefelhalogenide. 16. Dimethyliodsulfonium(IV)-Salze

Contributions to the Chemistry of Sulfur Halides. 16. Dimethyliodosulfonium(IV) Salts Some preparative methods of iodosulfonium(IV) salts, (CH₃)₂SI⁺AsF₆^? and (CH₃)₂SI⁺SbCl₆^?, are reported. These salts are stable up to ?20°C and they are characterized by Raman and n.m.r. spectroscopy.     

Die Schwingungsspektren des Chlortrimethylammonium-chlorids und -hexachloroantimonats(V)

Inhaitsübersicht. Die Schwingungsspektren von (CH₃)₃NCI₂ (I) und (CH₃)₃NCl⁺SbCI₆^– (II) wurden aufgenommen und im Hinblick auf die N—Cl-Bindungsverhältnisse diskutiert. The Vibrational Spectra of Chlorotrimethylammonium Chloride and Hexachloroantimonate(V) Abstract. The vibrational spectra of (CH₃)₃NCl₂ (I) und (CH₃)₃NCl⁺SbCl₆^– (II) are measured and discussed in view of the N-Cl bonds. Die IR-Spektren der nach [9] dargestellten Verbindungen wurden als Verreibungen in Nujol bzw. Hostaflonöl mit einem linear in Wellenzahlen registrierenden IR-Spektrophotometer PE 457 (Perkin Elmer) aufgenommen. Die Raman-Spektren wurden mit einem Coderg-Laser-Gerät PHO vermessen. Zur Anregung wurde die 4880 Å-Linie eines Argon-Gaslasers verwendet.     

Beiträge zur Chemie der Schwefel-Halogenide. 20. Di(methylthio)methyl- und Di(phenylthio)methylsulfonium-hexafluoroarsenat und -hexachloroantimonat

Contributions to the Chemistry of Sulfur Halides. 20. Di(methylthio)methyl- and Di(phenylthio)methylsulfonium Hexafluoroarsenate and Hexachloroantimonate Preparation and spectroscopic characterization of di(methylthio)methyl- and di(phenylthio)methylsulfonium salts CH₃S(SCH₃)₂⁺A^? and CH₃S(SC₆H₅)₂⁺A^? (A^? = AsF₆^?, SbCl₆^?) is reported. Complementary the crystal structure of di(methylthio)methylsulfonium hexafluoroarsenate has been determined.     

Über die Darstellung der Dimercapto(methyl)sulfonium-Salze[CH3S(SH)2]+AsF−6 und [CH3S(SH)2]+SbCl−6 und der Bis(chlorthio)Methylsulfonium-Salze [CH3S(SCI)2]+ AsF6−und [CH3S(SCL)2]+SbCl−6

On the Preparation of Dimercapto(methyl)Sulfonium Salts [CH₃S(SH)₂]⁺ AsF₆^? and [CH₃S(SH)₂]⁺SbCl₆^? and the Bis(chlorothio)methylsulfonium Salts [CH₃S(SCI)₂]⁺ AsF₆^? and [CH₃S(SCI)₂]⁺ SbCl₆^? The preparation of the dimercapto(methyl)sulfonium salts [CH₃S(SH)₂]⁺ AsF₆^? and [CH₃S(SH)₂]⁺SbCl₆^? from [CH₃SCl₂]⁺ salts and H₂S at 195 K is reported. The salts are stable below 210 K. They are characterized by additional Raman spektroscopic measurements of the isotopic labelled cations [CH₃S(SD)₂]⁺, [CH₃S(³⁴SH)₂]⁺ and [CH₃S(₃₄SD)₂]⁺. The dimercapto(methyl)sulfonium salts are transfered into bis(chlorthio)methylsulfonium salts by reaction with Cl₂ at 195 K.     

Isomerisation des ions C5H9O+ en phase gazeuse : migration 1,2 de methyle.

The potential energy profile associated to (CH₃)₂CCOCH₃^⊕ » (CH₃)₃CCO^⊕ » (CH₃)₃C^⊕ + CO is established and serves to discuss the metastable pinacolone ions characteristics.     

Thermally and electron-impact-induced rearrangements of dimethylthioncarbamates in gaseous phase

The thermally and electron-impact-induced rearrangements of the dimethylthioncarbamates to the dimethylthiolcarbamates are discussed. Owing to the competition with the ion fragmentation reactions in the mass spectrometric time, < 10^?6 seconds, the extent of the mass spectrometrically observed ion isomerization cannot be predicted from that of the thermal induced one. In the ion fragmentations of the non-rearranged molecular ions, it was found that the relative abundance of the ion (CH₃)₂NC?O^⊕ to the total ionization is larger than that of the ion (CH₃)₂NC?S^⊕. This is believed to be attributable to the differences in the dissociation energies of the C? S bond and the C? O bond and in the stabilities of the two ions.     

Polysulfonylamine. XL Darstellung von Silber(I)-disulfonylamid-Acetonitril-Komplexen. Röntgenstrukturanalytische und thermochemische Charakterisierung von Tetraacetonitrilsilber(I)-bis(dimesylamido)argentat(I) und von (1,1,3,3-Tetraoxo-1,3,2-benzodithiazolido)acetonitrilsilber(I)

Polysulfonyl Amines. XL. Preparation of Silver(I) Disulfonylamide Acetonitrile Complexes. Characterization of Tetraacetonitrilesilver(I) bis(dimesylamido)argentate(I) and (1,1,3,3-Tetraoxo-1,3,2-benzodithiazolido)acetonitrilesilver(I) by X-Ray Diffractometry and Thermal Analysis The following silver(I) disulfonylamides were prepared for the first time or by improved procedures: AgN(SO₂CH₃)₂ ( 2a ); AgN(SO₂C₆H₄-4-X)₂ with X = F ( 2b ), Cl ( 2c ), Br ( 2d ), CH₃ ( 2e ); silver(I) 1,2-benzenedisulfonimide AgN(SO₂)₂C₆H₄ ( 2f ). With acetonitrile, the salts 2a to 2e form (1/2) complexes AgN(SO₂R)· 2 CH₃CN ( 4a to 4e ), whereas 2f gives the (1/1) complex AgN(SO₂)₂C₆H · CH₃CN ( 4f ). The crystallographic data (at - 95°C) for the title compounds 4a and 4f are: 4a , space group C2/c, a = 1 967.6(4), b = 562.2(1), c = 2 353.0(5) pm, β = 102.21(2)°, V = 2.5440 nm³, Z = 4, D_x = 1.891 Mg m^?3; 4f , space group P2₁/m, a = 741.5(3), b = 980.4(4), c = 756.6(3) pm, β = 99.28(2)°, V = 0.5428 nm³, Z = 2, D_x = 2.246 Mg m^?3. 4a forms an ionic crystal [Ag(NCCH₃)₄]^⊕[Ag{N(SO₂CH₃)₂}₂]^? with a tetrahedrally coordinated silver atom (lying on a twofold axis) in the cation (225.3/225.7 pm for the two independent Ag? N distances, N? Ag? N 106.2—114.5°) and a linear-dicoordinated silver atom in the centrosymmetric anion (Ag? N 213.9 pm, two intraionic secondary Ag…O contacts 303.4 pm). 4f consists of uncharged molecules [C₆H₄(SO₂)₂N¹AgN²CCH₃] with crystallographic mirror symmetry (Ag? N¹ 218.8, Ag? N² 216.1 pm, N¹? Ag? N² 174.3°), associated into strands by intermolecular secondary silver-oxygen contacts (Ag…O 273.8 pm, O…Ag…O 175.6, N? Ag…O 91.9/88.2°). The thermochemical behaviour of 4f was investigated using thermogravimetry, differential scanning calorimetry (DSC), time- and temperature-resolved X-ray diffractometry (TXRD), and solution calorimetry. The desolvation process occurs in the temperature range from 60 to 200°C and appears to be complex, although no crystalline intermediate could be detected. The desolvation enthalpy at 298 K was found to be + 26.8(4) kJ mol^?1. 4a is desolvated in two steps at - 15 to 60°C and 60 to 95°C (DSC), suggesting the formation of AgN(SO₂CH₃) · CH₃CN as an intermediate.