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.     

Di(tert-butyl)diazomethan: Thermische Zersetzung und Einelektronen-Redox-Reaktionen

Di(tert-butyl)diazomethane: Thermal Decomposition and One-Electron Redox Reactions. Di(tert-butyl)diazomethane is a potential precursor for the still unknown, presumably sterically overcrowded tetrakis(tert-butyl)ethane and, therefore, re-investigated. Its (Hel) photoelectron spectrum exhibits a low first vertical ionization energy of only 7.45 eV. Based on the ionization pattern, both the thermal decomposition above 600 K under nearly unimolecular conditions as well as the N₂ elimination at the surface of contacts, [Ni_x/C]_∞, [Rh₄(CO)₁₂/SiO₂]_∞, [Rh_x/SiO₂]_∞, and [Ag₂CO₃]_∞ are analyzed in a flow-system. Heterogeneously catalyzed, N₂ is split off already at room temperature, but in contrast to results for sterically less shielded diazo compounds, no dimer is formed, and only mixtures of known di(tert-butyl)carbene-isomerization products are isolated. Cyclic voltammetry at 233 K using a glassy carbon electrode proves a reversible oxidation followed by N₂ elimination at higher temperatures and an irreversible reduction. On chemical oxidation, however, no paramagnetic species can be detected, whereas chemical reduction at a potassium metal mirror in a THF solution containing (2.2.2)cryptand, yields the radical anion characterized by ESR spectroscopy. Without a cation-chelating ligand, the radical anion of a hitherto unknown dimer, ((CH₃)₃C)₂C?N? N?N? N?C(C(CH₃)₃) ₂' ^?, is generated, which dissociates at higher temperature, forming ((CH₃)₃C)₂?N₂' ^?. This one-electron reduction product of di(tert-butyl)diazomethane can also be detected after quickly warming up a solution containing presumably the radical anion of the triphenylphosphane adduct ((CH₃)₃C)₂C?N? N? PPh₃' ^?. In one of these reduction reactions, a N₂ elimination is observed.     

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.     

Über die Darstellung von Di(i-propyl)thiosulfonium-Salzen

On the Preparation of Di(i-propyl)thiosulfonium Salts [1] The preparation of the mercaptosulfonium salts (i-C₃H₇)₂SSX⁺SbCl₆^? (X = H, D) and of the chlorothiosulfonium salts (i-C₃H₇)₂SSCl⁺MF₆^? (M = As, Sb) and (i-C₃H₇)₂SSSCl⁺SbCl₆^? is reported. They are formed by reaction of chlorinated or protonated (i-C₃H₇)₂S with excess H₂S or SCl₂ and S₂Cl₂. The thiosulfonium compounds are characterized by vibrational and NMR spectroscopic methods.     

Dihalogen(pentafluorphenyl)sulfonium(IV)-hexafluoroarsenat C6F5SX2+AsF6− (X = Cl,Br) und Kristallstruktur von Di(pentafluorphenyl)sulfan (C6F5)2S

Dihalogen(Pentafluorophenyl)sulfonium(IV) Hexafluoroarsenate C₆F₅SX₂⁺AsF₆^? (X = Cl, Br) and Crystal Structure of Di(pentafluorophenyl)sulfane (C₆F₅)₂S The preparation and spectroscopic characterisation of the halogensulfonium salts C₆F₅SCl₂⁺AsF₆^? and C₆F₅SBr₂⁺AsF₆^? is reported. The new salts are much more stable than their trifluoromethyl derivatives. In addition the crystal structure of (C₆F₅)₂S is reported. Space group P4₃2₁2, Z = 4, 478 unique observed diffractometer data, R_int. = 0.07, lattice constants: a = 569.0(5) pm, c = 3785.8(22) pm, V = 1225 times; 10^?30 m³.     

Polysulfonylamine. XLVI Molekülkomplexe von Di(organosulfonyl)aminen mit Dimethylsulfoxid und Triphenylphosphinoxid. Röntgenstrukturanalyse von Di(4-fluorbenzolsulfonyl)amin-Dimethylsulfoxid(2/1)

Polysulfonyl Amines. XLVI. Molecular Adducts of Di(organosulfonyl)amines with Dimethyl Sulfoxide and Triphenylphosphine Oxide. X-Ray Structure Determination of Di(4-fluorobenzenesulfonyl)amine-Dimethyl Sulfoxide(2/1) From equimolar solutions of the respective components in CH₂Cl₂/petroleum ether, the following crystalline addition compounds were obtained: (X? C₆H₄SO₂)₂NH …? OS(CH₃)₂, where X = H, 4? CH₃, 4? Cl, 4? Br, 4? I, 4? NO₂ or 3? NO₂; [(4? F? C₆H₄SO₂)₂NH]₂ · (OS(CH)₃)₂ ( 8 ); (4? I? C₆H₄SO₂)₂NH · OP(C₆H₅)₃. A (2/1) complex of (4? F? C₆H₄SO₂)₂NH with OP(C₆H₅)₃ could not be isolated. The solid-state structure of the (2/1) compound 8 is compared with the known structure of the (1/1) complex (CH₃SO₂)₂NH · OS(CH₃)₂. The crystallographic data for 8 at ?95°C are: monoclinic, space group C2/c, a = 2 369.9(13), b = 1 006.8(4), c = 2 772.6(13) pm, β = 110.71(4)°, U = 6.187 nm³, Z = 8. Two N? H …? O hydrogen bonds with N …? O 275 and 280 pm connect the disulfonylamine molecules with the dimethyl sulfoxide molecule. The O atom of the latter has a trigonal-planar environment consisting of the S atom and the two hydrogen bond H atoms.     

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.     

Dialkyltriazaniumsalze, 3. Mitt.: Die IR- und1H-NMR-Spektren von Dimethyl-, Diäthyl- und Cyclotetramethylentriazaniumchlorid

The IR- and¹H-NMR spectra of [(CH₃)₂N₃H₄]⁺Cl^?, [(C₂H₅)₂N₃H₄]⁺Cl^? and [(CH₂)₄N₃H₄]⁺Cl^? are reported and discussed. Evidence for the structure of 2,2-dialkyltriazaniumsalts is given.¹H-NMR measurements give evidence for interand intramolecular hydrogen bridges in d₆-dimethylsulfoxide and water.     

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.     

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.     

Darstellung und spektroskopische Eigenschaften der gemischtvalenten Di(phthalocyaninato)lanthanide(III)

Synthesis and Spectroscopical Properties of the Mixed-Valent Di(phthalocyaninato)lanthanides(III) Green di(phthalocyaninato)lanthanide(III), [M(Pc)₂] (M = rare earth metal ion: La‥(-Ce, Pm)‥Lu) is prepared by anodic oxidation of (ⁿBu₄N)[M(Pc^2?)₂] dissolved in CH₂Cl₂/(ⁿBu₄N)ClO₄. The UV-Vis-NIR spectra show intense π-π* transitions at ? 15000 cm^?1 and 31000 cm^?1, typical for Pc^2? ligands. Bands at ? 11000 cm^?1 and 22000 cm^?1 indicate the equal presence of a Pc^? π-radical. The metal dependent NIR band between 4000 and 9000 cm^?1 is characteristic for these mixed-valent complexes and assigned to an intervalence transition (b₁ → a₂; D_4d symmetry). Most bands are shifted linearly with the M^III radius. In the IR and resonance Raman (r.r.) spectra the typical vibrations of the Pc^? π-radical are dominant. These are essentially metal independent excepting the C? C and C? N vibrations of the inner (CN)₈ ring. The sym. M? N stretching vibration between 141 (La) and 168 cm^?1 (Lu) is selectively r.r.-enhanced when excited with 1064 nm.     

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^?.     

(CH3)2SBr2 – einige Reaktionen und Strukturen

(CH₃)₂SBr₂ – Reactions and Structures (CH₃)₂SBr₂ ( 1 ) is a donor acceptor complex (8-S-3 + 10-Br-2) which reacts with (CH₃)₂S(?O)NSi(CH₃)₃ to yield [(CH₃)₂S(O)?N? S(CH₃)₂]⁺Br^? ( 2 ). With SbBr₃ (CH₃)₂SBr⁺SbBr₄^? ( 3 ) can be isolated. 1 crystallizes monoclinic in the space group P2₁/c with a = 733.8, b = 734.2, c = 1132.7 pm, β = 92.8° and Z = 4. 2 crystallizes in the orthorhombic space group Pnma with a = 967.2, b = 793.3, c = 1168.3 pm and Z = 4. The SBr and BrBr force constants of 1 are compared with those of S₂Br₂, 3 and Br₂ resp. The nmr and mass spectra of 1 and 2 are communicated.     

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.     

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.     

Absolute Rate Constants for the Addition of Cyanomethyl (·CH2CN) and (tert-Butoxy)carbonylmethyl (·CH2CO2C(CH3)3) radicals to alkenes in solution

Absolute rate constants and their temperature dependence were determined by time-resolved electron spin resonance for the addition of the radicals ·CH₂CN and ·CH₂CO₂C(CH₃)₃ to a variety of mono- and 1,1-disubstituted and to selected 1,2- and trisubstituted alkenes in acetonitrile solution. To alkenes CH₂?CXY, ·CH₂CN adds at the unsubstituted C-atom with rate constants ranging from 3.3·10³ M ^?1S ^?1 (ethene) to 2.4·10⁶ M ^?1S ^?1 (1,1-diphenylethene) at 278 K, and the frequency factors are in the narrow range of log (A/M ^?1S ^?1) = 8.7 ± 0.3. ·CH₂CO₂C(CH₃)₃ shows a very similar reactivity with rate constants at 296 K ranging from 1.1·10⁴ M ^?1S ^?1 (ethene) to 10⁷ M ^?1S ^?1 (1,1-diphenylethene) and frequency factors log (A/M ^?1S ^?1) = 8.4 ± 0.1. For both radicals, the rate constants and the activation energies for addition to CH₂?CXY correlate well with the overall reaction enthalpy. In contrast to the expectation of an electro- or ambiphilic behavior, polar alkene-substituent effects are not clearly expressed, but some deviations from the enthalpy correlations point to a weak electrophilicity of the radicals. The rate constants for the addition to 1,2- and to trisubstituted alkenes reveal additional steric substituent effects. Self-termination rate data for the title radicals and spectral properties of their adducts to the alkenes are also given.     

Anion-controlled redistribution reactions in the system C3Cl3+A−/(CH3)3SiN(CH3)2

Transmination reactions of the 4z-exchange type between C₃Cl₃⁺A^? and (CH₃)₃SiN(CH₃)₂ are introduced as a novel mode of aromatic substitution at the C₃⁺-core. The extent of transamination can be controlled by appropriate choice of counterion A^?.     

Diiod(methylthio)gallan. Darstellung und reaktivität

Different synthetic routes for the preparation of diiodo(methylthio)gallane are given. Some reactions of this compound with Lewis bases, such as O(CH₃)₂, S(CH₃)₂, S₂(CH₃)₂, N(CH₃)₃, P(CH₃)₃, and other compounds, such as CH₃I, CH₃OH, C₂H₅OH, C₂H₅SH, i-C₃H₇SH, and C₂H₅SeH are investigated. Spectra and some physical and chemical properties of the new compounds are reported. The structure of diiodo(methylthio)gallane is discussed in view of some interesting differences of this molecule in solution and in crystal form.     

Low-spin Manganphthalocyanine: Darstellung,Eigenschaften und elektronisches Raman-Spektrum von Di(cyano)phthalocyaninatomanganat(III) und -(II)

Low Spin Manganese Phthalocyanines: Preparation, Properties and Electronic Raman Spectrum of Di(cyano)phthalocyaninatomanganate(III) and -(II) . Iodophthalocyaninatomanganese(III) reacts with cyanide in acetone to yield di(cyano)phthalocyaninatomanganate(II), in dichloromethane, however di(cyano)phthalocyaninatomanganate(III) is formed. Both complexes are isolated as (n-Bu₄N)-salts. In the cyclovoltammogram the redox couple Mn^II/Mn^III is attributed to E_1/2 = - 0.22 V and the first ringoxidation Pc(2 -)/Pc(1 -) to E_1/2 = 0.75 V. The paramagnetic salts have magnetic moments (μ_eff = 2.11 resp. 2.95 B.M.) typical for the low spin ground state of Mn^II resp. Mn^III (S = 1/2 resp. 1). The uv-vis-nir spectra are discussed. Comparison with the dicyano-complexes of Cr^III, Fe^II/III and Co^III indicates that the multiple “extra bands” between 4 and 23 kK should be assigned to spin allowed trip-multiplets. The vibrational spectra are discussed. ν_as(Mn? C)(a_2u) is found at 350 cm^?1, ν_as(C? N)(a_2u; cyanide) at 2 092 (Mn^II) and 2 114 cm^?1 (Mn^III). The Raman spectra are dominated by resonance Raman(RR) effects. With variable-wavelength excitation polarized, depolarized and anomalously polarized vibrations assigned to phthalocyanine skeletal modes are selectively RR-enhanced for the Mn^II complex. Intensive lines between 1 650 and 3 300 cm^?1 are due to combinations and overtones of the a_2g vibrations at 1 492 and 1 602 cm^?1. In the 10 K Raman spectrum of (n-Bu₄N)[Mn(CN)₂Pc(2 -)] intraconfigurational transitions Γ₁ → Γ₄ and Γ₁ → Γ₃, Γ₅ resulting from the splitting of the ³T_1g ground state of Mn^III (O_h symmetry) by spin-orbit coupling are observed as anomalously polarized and depolarized lines at 172 and 287 cm^?1.     

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.