Synthesen und Eigenschaften von Tris(perfluoralkyl)arsen- und -antimon(III,V)-Verbindungen

Preparations and Properties of Tris(perfluoroalkyl) Arsenic and Antimony(III, V) Compounds As(R_f)₃ and Sb(R_f)₃ (R_f?C₂F₅, C₄F₉, C₆F₁₃) are prepared in good yields by the polar reactions of AsCl₃ and SbCl₃ with bis(perfluoroalkyl) cadmium compounds as colourless liquids or solids. The oxidation of As(C₂F₅)₃ and Sb(C₂F₅)₃ with XeF₂ gives the difluorides M(C₂F₅)₃F₂ (M?As, Sb). As(C₂F₅)₃Cl₂ is prepared by chlorination of As(C₂F₅)₃ in the presence of AlCl₃, while Sb(C₂F₅)₃Cl₂ is formed in the reaction of Sb(C₂F₅)₃F₂ with (CH₃)₃SiCl. During the reaction of M(C₂F₅)₃F₂ with (CH₃)₃SiBr ¹⁹F-NMR spectroscopic evidence is found for M(C₂F₅)₃ Br₂. The thermal decompositions of M(C₂F₅)₃F₂ mainly yield C₄F₁₀ and M(C₂F₅)F₂, while the thermal decompositions of M(C₂F₅)₃Cl₂ yield M(C₂F₅)₂Cl and C₂F₅Cl. The properties and spectroscopic data of the new compounds are described.     

Perfluororganotellur-Verbindungen: Neue Untersuchungen zur Darstellung von Te(Rf)2 und CH3TeRf (Rf = C2F5, C3F7, C6F5)

Perfluoroorgano Tellurium Compounds: New Investigations on the Preparation of Te(R_f)₂ and CH₃TeR_f (R_f = C₂F₅, C₃F₇, C₆F₅) Methyl(perfluoroorgano) tellurium and bis(perfluoroorgano) tellurium compounds are synthesized in high yields from the photochemical or the thermal reactions of (CH₃)₂ Te with perfluoroorgano iodides in the presence of (C₂H₅)₃N. They are isolated in pure states. Another general method for the preparation of bis(perfluoroorgano) tellurium is the thermal reaction of TeCl₄ with bis(perfluoroorgano) mercury. The preparations and properties of the partially new compounds are described.     

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.     

Synthesis,Properties, and Application of Tetrakis(pentafluoroethyl)gallate, [Ga(C2F5)4]−

Weakly coordinating anions (WCAs) are important for academic reasons as well as for technical applications. Tetrakis(pentafluoroethyl)gallate, [Ga(C₂F₅)₄]^?, a new WCA, is accessible by treatment of [GaCl₃(dmap)] (dmap=4‐dimethylaminopyridine) with LiC₂F₅. The anion [Ga(C₂F₅)₄]^? proved to be reluctant towards deterioration by aqueous hydrochloric acid or lithium hydroxide. Various salts of [Ga(C₂F₅)₄]^? were synthesized with cations such as [PPh₄]⁺, [CPh₃]⁺, [(O₂H₅)₂(OH₂)₂]²⁺, and [Li(dec)₂]⁺ (dec=diethyl carbonate). Thermolysis of [(O₂H₅)₂(OH₂)₂][Ga(C₂F₅)₄]₂ gives rise to a dihydrate of tris(pentafluoroethyl)gallane, [Ga(C₂F₅)₃(OH₂)₂]. All products were characterized by NMR and IR spectroscopy, mass spectrometry, X‐ray diffraction, and elemental analysis. Furthermore, an outlook for the application of [Li(dec)₂][Ga(C₂F₅)₄] as a conducting salt in lithium‐ion batteries is presented.     

Kristallstruktur-Untersuchungen von Bis(pentafluorphenyl)tellurdihalogeniden (C6F5)2TeHal2 (Hal = Cl,Br)

Crystal Structure Determinations of Bis(pentafluorophenyl)tellurium Dihalides (C₆F₅)₂TeHal₂ (Hal = Cl, Br) Bis(pentafluorophenyl)telluriumdichloride and bis(pentafluorophenyl)telluriumdibromide crystallize at 10°C or 20°C from CH₂Cl₂ or CHCl₃ solution in the monoclinic space group P2₁/c with a = 649.5(1) pm, b = 1 275.6(2) pm, c = 1 816.2(5) pm, β = 92.89(2)° for (C₆F₅)₂TeCl₂ and a = 694.4(1) pm, b = 1 579.1(2) pm, c = 1 423.4(1) pm, β = 90.22(2)° for (C₆F₅)₂TeBr₂ with four formula units per each unit cell.     

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.     

Pentafluorphenyliod(III)-Verbindungen. 2. Fluor-Aryl Substitution an Iodtrifluorid: Synthese von Pentafluorphenylioddifluorid C6F5IF2 und Bis(pentafluorphenyl)iodonium Pentafluorphenylfluoroboraten [(C6F5)2I]+[(C6F5)nBF4−n]−

Pentafluorophenyliodine(III) Compounds. 2. Fluorine-Aryl Substitution Reactions on Iodinetrifluoride: Synthesis of Pentafluorophenyliodinedifluoride C₆F₅IF₂ and Bis(pentafluorophenyl)iodonium Pentafluorophenylfluoroborates[(C₆F₅)₂I]⁺[(C₆F₅)_nBF_4?n]^? Mono- and disubstitution can be achieved in the fluorine-aryl substitution reaction on the low-temperature phase IF₃ in CH₂Cl₂ at ?78°C depending on the aryl transfer reagent. With B(C₆F₅)₃ [(C₆F₅)₂I]⁺ [(C₆F₅)_nBF_4?n]^? (68% yield) and with Cd(C₆F₅)₂ C₆F₅IF₂ (97% yield) is obtained whereas with C₆F₅SiMe₃ no fluorine-aryl substitution takes place on IF₃ even under basic conditions (EtCN or F^? addition). At ?78°C in EtCN solution IF₃ does not disproportionate but attacks the solvent under formation of HF.     

The preparations and properties of tris(perfluoroorgano)bismuth compounds Bi(Rf)3 (Rf = CF3, C2F5, n-C3F7, n-C4F9, n-C6F13, n-C8 F17, C6F5)

Tris(perfluoroorgano)bismuth compounds Bi(R_f)₃ (R_f = CF₃, C₂F₅, n-C₃F₇, n-C₄F₉, n-C₆F₁₃, n-C₈F₁₇, C₆F₅) are easily prepared in high yields from the reactions of perfluoroorganocadmium complexes with BiCl₃, or BiBr₃ in aprotic solvents. The perfluoroorganobismuth halides intermediates in these reactions have been detected by NMR spectroscopy.     

Theoretical Exploration of Stereochemical Nonrigidity for RfCo（PF3）x（CO）4-x（Rf=CF3, C2F5, C3F7, x=0-4）

The stereochemical nonrigidity of RfCo（PF3）x（CO）4-x（Rf=CF3,C2F5,C3F7,x=0-4） was studied at the theoretical level of B3LYP/6-31 1＋G^＊ via Gaussian 09.The intramolecular rearrangements in these penta-coordinated compounds are mainly caused by the vibrations of perfluoroalkyl groups.All the barriers along the reaction coordinate are less than 66.9 kJ/mol,which indicates that the rearrangements are kinetically favorable and hard to elucidate by experiment.Besides,ligand PF3 is a ligand similar to CO,the energy difference between the reactant and product is small.     

Synthese und Eigenschaften von Diethyldithiocarbaminsäureperfluororganylestern, (C2H5)2NC(S)SRf (Rf = CF3, C2F5, i‐C3F7, n‐C4F9, C6F5)

Syntheses and Properties of Perfluoroorgano Esters of the Diethyldithiocarbamic Acid, (C₂H₅)₂NC(S)SR_f (R_f = CF₃, C₂F₅, i‐C₃F₇, n‐C₄F₉, C₆F₅) Tetraethylthiuram disulfide reacts under different conditions with perfluoroorgano silver(I), AgR_f, and perfluoroorgano cadmium compounds, Cd(R_f)₂, to give the corresponding perfluoroorgano esters of diethyldithiocarbamic acid, (C₂H₅)₂NC(S)SR_f (R_f = CF₃, C₂F₅, i‐C₃F₇, n‐C₄F₉, C₆F₅), and metal diethyldithiocarbamates, AgSC(S)N(C₂H₅)₂ and Cd[SC(S)N(C₂H₅)₂]₂. The mechanisms of the reactions with AgR_f and Cd(R_f)₂ are discussed.     

ChemInform Abstract: Synthesis and Crystal Structure of [Re2Br4(Te2)(TeBr)2 (TeBr2)2], a Dinuclear Complex with Te22-, TeBr-, and TeBr2 Ligands.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

ChemInform Abstract: Crystal Structure and Sodium Environments in Sodium Tetratellurite,Na2Te4O9, and Sodium Tellurite,Na2TeO3, by X-Ray Crystallography and Sodium-23 NMR.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

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.     

ChemInform Abstract: Ta5(S,Te)2: Microporous Tantalum with Chalcogen-Coated Inner Surfaces.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

ChemInform Abstract: Hexatellurium Rings in Coordination Polymers and Molecular Clusters: Synthesis and Crystal Structures of [M(Te6)]X3 (M: Rh,Ir; X: Cl,Br, I) and [Ru2(Te6)] (TeBr3)4(TeBr2)2.

Black crystals of [Rh(Te₆)]Br₃ (I), [Rh(Te₆)]I₃ (II), [Ir(Te₆)]Cl₃ (III), [Ir(Te₆)]Br₃ (IV), and [Ir(Te₆)]I₃ (V) are prepared from stoichiometric mixtures of Rh or Ir, Te, and TeX₄ (X: Cl, Br, I; evacuated silica tube, 300—350 °C, 7 d).     

Neue Oxonium-Bromochalkogenate(IV) — Darstellung,Struktur und Eigenschaften von [H3O][TeBr5] · 3C4H8O2 und [H3O]2[SeBr6]

New Oxonium Bromochalcogenates(IV) — Synthesis, Structure, and Properties of [H₃O][TeBr₅] · 3 C₄H₈O₂ and [H₃O]₂[SeBr₆] Dark red crystals of the composition [H₃O][TeBr₅] · 3 C₄H₈O₂ ( 1 ) were isolated from a saturated solution of TeBr₄ in 1,4-dioxane containing a small amount of water. In this compound (space group P2₁/m, a = 8.922(4) Å, b = 13.204(7) Å, c = 9.853(5) Å, β = 91.82(4)° at 150 K) a square pyramidal [TeBr₅]^? anion has been isolated for the first time. The coordination sphere of the anion is completed to a distorted octahedron by weak interaction with a dioxane molecule of the cationic system. The [H₃O]⁺ cations are connected to chains by dioxane molecules. At room temperature the compound is stable only in its mother liquor. Crystalline [H₃O]₂[SeBr₆] ( 2 ) (space group Fm3m, a = 10.421(1) Å at 170 K) is a bromoselenous acid of high symmetry. The [H₃O]⁺ ion is only weakly coordinated by Br atoms of the anion. The anions are isolated octahedral [SeBr₆]^2? units. The structure is isotypic to the K₂[PtCl₆] structure. Despite being a halogenochalcogen(IV) acid, 2 exhibits a remarkable thermal stability. Both oxonium compounds were characterized by single-crystal X-ray structure analyses. Vibrational spectra of 2 are reported.     

Synthese und Struktur von [(Ph3C6H2)Te]2, [(Ph3C6H2)Te(AuPPh3)2]PF6 und [(Ph3C6H2)TeAuI2]2

Synthesis and Structure of [(Ph₃C₆H₂)Te]₂, [(Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ and [(Ph₃C₆H₂)TeAuI₂]₂ [(2,4,6-Ph₃C₆H₂)Te]₂ reacts with Ph₃PAu⁺ to yield [2,4,6-Ph₃C₆H₂TeAuPPh₃₂]PF₆ which can be oxidized by I₂ to form the gold(III) complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂. [(2,4,6-Ph₃C₆H₂)Te]₂ crystallizes in the monoclinic space group P2₁/c with a = 810.6(2); b = 2026.5(5); c = 2260.6(7) pm; β = 99.23(3)° and Z = 4. In the crystal structure the ditelluride exhibits a dihedral angle C11? Te1? Te2? C21 of 66.1(2)°. The distance Te1? Te2 is 269.45(6) pm. In the cation of the triclinic complex [(2,4,6-Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ (space group P1 ; a = 1197.4(3); b = 1457.2(4); c = 1680.0(6) pm; α = 84.69(3)°; β = 85.11(3)°; γ = 75.54(3)°; Z = 2) a pyramidal skeleton RTeAu₂ with distances Te? Au = 259.2(1) and 257.8(2) pm and Au? Au = 295.3(1) pm is present. [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ crystallizes in the triclinic space group P1 with a = 1086.3(3); b = 1462.9(6); c = 1654.2(2) pm; α = 85.25(2)°; β = 87.44(1)°; γ = 80.90(3)°; Z = 2. In the centrosymmetrical dinuclear complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ the Au atoms exhibit a square-planar coordination by two iodine atoms and two tellurolate ligands. The tellurolate ligands form symmetrical bridges with distances Te? Au = 260.0 pm. The distances Au? I are in the range of 260.3(1) and 263.7(1) pm.