Untersuchungen zu Synthese und Reaktionen von Fluorphenylquecksilber-Derivaten mit den Liganden 2-FC6H4, 2,6-F2C6H3 und 2,4,6-F3C6H2

Investigations on Syntheses and Reactions of Fluorophenylmercury Compounds with the Ligands 2-FC₆H₄, 2,6-F₂C₆H₃, and 2,4,6-F₃C₆H₂ 2,6-F₂C₆H₃HgCl and 2,4,6-F₃C₆H₂HgCl are synthesized via the reactions of the corresponding phenylmagnesium compounds and HgCl₂. 2-FC₆H₄HgCl is selectively obtained only in a reaction involving intermediately formed Cd(2-FC₆H₄)₂. The diphenylmercury derivative Hg(2,4,6-F₃C₆H₂)₂ is obtained while stirring a dichloromethane solution of 2,4,6-F₃C₆H₂HgCl for several days. The direct mercuration of 1,3,5-trifluorobenzene with Hg(OCOCF₃)₂ yields, depending on the stoichiometry, 2,4,6-trifluorophenylmercury trifluoroacetate and 1,3-bis(trifluoroacetatomercuri)-2,4,6-trifluorobenzene which is converted into the corresponding chloromercuri derivative by treatment with hydrochloric acid in CH₃CN. As a product of the reaction of 1,3,5-trifluorobenzene and HgO in CH₃COOH only 2,4,6-trifluorophenylmercury acetate is isolated although spectroscopic evidence has been found for double and triple mercurated derivatives. All compounds are characterized by elemental analyses, nmr and mass spectra. The reaction of Hg(2,4,6-F₃C₆H₂)Cl and Cd(CF₃)₂ · 2 CH₃CN gives Hg(2,4,6-F₃C₆H₂)CF₃ which slowly dismutates in CH₂Cl₂ solution into Hg(2,4,6-F₃C₆H₂)₂ and Hg(CF₃)₂. The ligand exchange of Hg(2,4,6-F₃C₆H₂)₂ and TeCl₄ selectively gives Te(2,4,6-F₃C₆H₂)₂Cl₂ and Hg(2,4,6-F₃C₆H₂)Cl. Transmetalations of Hg(2,4,6-F₃C₆H₂)₂ and gallium or tin give NMR spectroscopic evidence for the new derivates Ga(2,4,6-F₃C₆H₂)₃ and Sn(2,4,6-F₃C₆H₂)₄.     

Mono‐ and Perfluoroaryliodine(III) Cyano Compounds – Synthesis,Reactivity, and Structure

C₆F₅I(CN)₂ and x‐FC₆H₄I(CN)₂ (x = 2, 3, 4) were isolated from reactions of the corresponding aryliodine difluorides ArIF₂ and a stoichiometric excess of Me₃SiCN in CCl₃F (0 °C) or CH₂Cl₂ (20 °C), respectively. In addition, x‐FC₆H₄I(CN)₂ compounds were synthesized in good yields on alternative routes, namely from 3‐ or 4‐FC₆H₄I(OC(O)CH₃)₂ or 4‐FC₆H₄I(OC(O)CF₃)₂ or from 4‐FC₆H₄IO and Me₃SiCN in CH₂Cl₂ at 20 °C. In the 1 : 1 reaction of C₆F₅IF₂ and Me₃SiCN a lower temperature was necessary to suppress partial disubstitution and to obtain the first example of a new type of aryliodine(III) cyanide compounds, C₆F₅I(CN)F. 4‐FC₆H₄I(CN)F could be isolated from the equimolar reaction of 4‐FC₆H₄IF₂ and Me₃SiCN in CH₂Cl₂ even at 20 °C. The new products were characterized by multi‐NMR and Raman spectroscopy. The molecular structures of C₆F₅I(CN)₂, 3‐ and 4‐FC₆H₄I(CN)₂, C₆F₅I(CN)F, and 4‐FC₆H₄I(CN)F are discussed and compared with that of C₆F₅IF₂. The reactivity of C₆F₅I(CN)F towards fluoride acceptors EF_n (BF₃, AsF₅) and R_xEX_?x (C₆F₅SiF₃, C₆H₅SiF₃, C₆H₅PF₄, Me₃SiCl, Me₃SiC₆F₅) were investigated and showed differing reaction patterns (fluoride abstraction, aryl transfer, chloride transfer). Besides the molecular entities C₆F₅I(CN)F and C₆F₅I(CN)Cl, the corresponding iodonium salts [C₆F₅(CN)I][BF₄] and [C₆F₅(CN)I][AsF₆] were isolated. The thermal stability of ArI(CN)₂ and ArI(CN)F, neat and in solution, as well as the reactivity of 4‐FC₆H₄I(CN)₂ towards the Lewis acid BF₃ are reported.     

Acetylenic derivatives of metal carbonyls of the triad Fe,Ru, Os—XI Mass spectra of some binuclear complexes

The mass spectra of the following acetylenic derivatives of iron, ruthenium and osmium carbonyls are reported: the iron compounds Fe₂(CO)₆[C₂(C₆H₅)s₂]₂, Fe₂(CO)₆[C₂(CH₃)₂]₂ and Fe₂(CO)₆[C₂(C₂H₅)₂]₂, the ruthenium compounds Ru₂(CO)₆[C₂(C₆H₅)₂]₂, and Ru₂(CO)₆[C₂(CH₃)₂]₂ and the osmium compounds Os₂(CO)₆[C₂(C₆H₅)₂]₂, Os₂(CO)₆[C₂HC₆H₅]₂ and Os₂(CO)₆[C₂(CH₃)₂]₂. Iron compounds exhibit breakdown schemes where binuclear, mononuclear and hydrocarbon ions are present. On the other hand, ruthenium and osmium compounds fragment in a similar way and give rise to singly and doubly charged binuclear ions. Phenylic derivatives of ruthenium and osmium also give weak triply charged ions. The results are discussed in terms of relative strengths of the metal-metal and metal-carbon bonds.     

Reactions of metal carbonyl derivatives X. The synthesis and reactivity of some dinuclear derivatives of iron containing both bridging carbonyls and bridging phosphido or sulphido groups

The tertiary phosphine π-C₅H₅Fe(CO)₂P(C₆H₅)₂ reacts with a suspension of Fe₂(CO)₉ in benzene to give the dinuclear complex π-C₅H₅Fe₂P(C₆H₅)₂(CO)₆. This compound is also obtained by nucleophilic attack of [π-C₅H₅Fe(CO)₂]⁻ on Fe(CO)₄-[P(C₆H₅)₂Cl] in tetrahydrofuran. Irradiation of a benzene solution of π-C₅H₅Fe₂-P(C₆H₅)₂(CO)₆ with ultraviolet light affords π-C₅H₅Fe₂P(C₆H₅)₂(CO)₅ which contains both a bridging carbonyl and a bridging phosphido group. The unstable bridged sulphido derivatives π-C₅H₅Fe₂SR(CO)₆ (R = CH₃ and C₆H₅) and π-C₅H₅Fe₂(t-C₄H₉S)(CO)₅ are similarly obtained employing π-C₅H₅Fe(CO)₂SR as ligand. The reactions of π-C₅H₅Fe₂P(C₆H₅)₂(CO)₅ with tertiary phosphines and phosphites yield three types of products depending on the reaction conditions and the ligand involved. Examples include π-C₅H₅Fe₂P(C₆H₅)₂(CO)₄P(C₆H₅)₃, a mono-substituted derivative of π-C₅H₅Fe₂P(C₆H₅)₂(CO)₅, and π-C₅H₅Fe₂P(C₆H₅)₂(CO)₅P(C₂H₅)₃ and π-C₅H₅Fe₂P(C₆H₅)₂(CO)₄[P(OCH)₃)₃]₂, mono- and bis-substituted derivatives of π-C₅H₅Fe₂P(C₆H₅)₂(CO)₆, respectively. The reaction of π-C₅H₅Fe₂P(C₆H₅₂(CO)₅ with (C₆H₅)₂PCH₂P(C₆H₅)₂ in benzene under reflux affords [π-C₅H₅Fe₂P(C₆H₅)₂(CO)₄](C₆H₅)₂PCH₂P(C₆H₅)₂ in which the ditertiary phosphine bridges two iron atoms.     

Untersuchungen an Polyhalogeniden. XXII [1]. Dimethyldiphenylammoniumpolyiodide (Me2Ph2N)In mit n = 3, 13/3, 6, 8: Darstellung und strukturelle Charakterisierung eines Triiodids (Me2Ph2N)I3, Tridecaiodids (Me2Ph2N)3I13, Dodecaiodids (Me2Ph2N)2I12 und Hexadecaiodids (Me2Ph2N)2I16

Studies of Polyhalides. 22. On Dimethyldiphenylammoniumpolyiodides (Me₂Ph₂N)I_n with n = 3, 13/3, 6, and 8: Preparation and Crystal Structures of a Triiodide (Me₂Ph₂N)I₃, Tridecaiodide (Me₂Ph₂N)₃I₁₃, Dodecaiodide (Me₂Ph₂N)₂I₁₂, and Hexadecaiodide (Me₂Ph₂N)₂I₁₆ The new compounds [(CH₃)₂(C₆H₅)₂N]I₃, [(CH₃)₂(C₆H₅)₂N]₃I₁₃, [(CH₃)₂(C₆H₅)₂N]₂I₁₂ and [(CH₃)₂(C₆H₅)₂N]₂I₁₆ have been prepared by the reaction of dimethyldiphenylammonium iodide [(CH₃)₂(C₆H₅)₂N]I with iodine I₂ in ethanol. Their crystal structures have been determined by single crystal X-ray diffraction methods. The structure of the triiodide may be described as a layerlike packing of pairs of nearly linear symmetric anions and tetraedral cations. The tridecaiodide forms zig-zag chains of iodide ions and iodine molecules with the iodide ion also weakly coordinated by two pentaiodide groups. The dodecaiodide is built from two pentaiodide-groups, which are bridged by an iodine molecule and connected with secondary bonds forming double chains. The hexadecaiodide ion forms layers built up from two heptaiodide groups and one iodine molecule. Thus the dimethyldiphenylammonium cation stabilizes a unique series of polyiodides of extraordinary composition and structure.     

Präparation und röntgenographische Charakterisierung der Verbindungen Ca3M2Ga2 (M = Pd,Pt) und Ca3M2Ga3 (M = Rh,Ir)

Preparation and Crystal Structures of the Compounds Ca₃Pd₂Ga₂, Ca₃Pt₂Ga₂, Ca₃Rh₂Ga₃, and Ca₃Ir₂Ga₃ The new compounds Ca₃Pd₂Ga₂, Ca₃Pt₂Ga₂, Ca₃Rh₂Ga₃, and Ca₃Ir₂Ga₃ were prepared by heating appropriate mixtures of the elements under an Argon-atmosphere. The results of the structure analysis of single crystals by means of X-ray diffraction are given in the section “Inhaltsübersicht”. Ca₃Pd₂Ga₂ and Ca₃Pt₂Ga₂ are isotypic and form the Y₃Rh₂Si₂ type structure (Pbcm), where the platinium metals have a trigonal environment consisting of Ga-atoms. The isotypic compounds Ca₃Rh₂Ga₃ and Ca₃Ir₂Ga₃ (Pbcm) form a new type of structure, which is related to the Y₃Rh₂Si₂ type with a distorted tetrahedral surrounding of Ga-atoms for Rh (resp. Ir).     

Die thermodynamische Stabilität der Molekeln Pd6Cl12, Pd6Br12 und Pt6Cl12

Thermodynamic Stability of Pd₆Cl₁₂, Pd₆Br₁₂, and Pt₆Cl₁₂ Molecules Vapour pressure data of PdCl₂ and PdBr₂ taken from the literature have been used to get new informations regarding the vapourization of Pd₆Cl₁₂ molecules. Using mixtures of PdCl₂ and AgBr as source materials, besides Pd₆Cl₁₂ molecules the vapourization of Pd₆Cl_12-nBr_n with n = 1 – 8 has been observed in a mass spectrometer. Semi quantitative observations concerning the vapourization of Pt₆Cl₁₂ molecules from a PtCl₂ solid are reported. Heats of formation and standard entropy data for the molecules Pd₆Cl₁₂, Pd₆Br₁₂ and Pt₆Cl₁₂ are given.     

Zur Kenntnis der Dialkalimetalldichalkogenide β-Na2S2, K2S2, α-Rb2S2, β-Rb2S2, K2Se2, Rb2Se2, α-K2Te2, β-K2Te2 und Rb2Te2

On Dialkali Metal Dichalcogenides β-Na₂S₂, K₂S₂, α-Rb₂S₂, β-Rb₂S₂, K₂Se₂, Rb₂Se₂, α-K₂Te₂, β-K₂Te₂ and Rb₂Te₂ The first presentation of pure samples of α- and β-Rb₂S₂, α- and β-K₂Te₂, and Rb₂Te₂ is described. Using single crystals of K₂S₂ and K₂Se₂, received by ammonothermal synthesis, the structure of the Na₂O₂ type and by using single crystals of β-Na₂S₂ and β-K₂Te₂ the Li₂O₂ type structure will be refined. By combined investigations with temperature-dependent Guinier-, neutron diffraction-, thermal analysis, and Raman-spectroscopy the nature of the monotropic phase transition from the Na₂O₂ type to the Li₂O₂ type will be explained by means of the examples α-/β-Na₂S₂ and α-/β-K₂Te₂. A further case of dimorphic condition as well as the monotropic phase transition of α- and β-Rb₂S₂ is presented. The existing areas of the structure fields of the dialkali metal dichalcogenides are limited by the model of the polar covalence.     

Kryometrische Untersuchungen. IV. Lösungen von oxidischen Mo6+- und Cr6+-Verbindungen in geschmolzenem K2Cr2O7 und KNO3

The depression of freezing point of molten K₂Cr₂O₇ and KNO₃ as solvents was measured after addition of small concentrations of the following compounds: to K₂Cr₂O₇: MoO₃, CrO₃, (NH₄)₂CrO₄, K₂MoO₄, Na₂MoO₄, Li₂MoO₄, and Na₂Mo₂O₇, respectively; to KNO₃: CrO₃, (NH₄)₂Cr₂O₇ K₂Cr₂O₇, K₂CrO₄ and MoO₃, (NH₄)₆(Mo₇O₂₄) · 4 H₂O, K₂Mo₂O₇, K₂MoO₄, Na₂MoO₄ and Li₂MoO₄, respectively. It could be concluded from the measured values of the freezing point depression if a reaction between solvent and solute took place.     

The chemistry of chromyl fluoride III. Reactions with inorganic systems

Reactions of CrO₂F₂ with MF or MF₂ gave the corresponding M₂CrO₂F₄ and MCrO₂F₄ fluorochromates. With the Lewis Acids (SO₃, TaF₅, SbF₅) and (CF₃CO)₂O known and new chromyl compounds [CrO₂(CF₃COO)₂, CrO₂(SO₃F)₂, CrO₂FTaF₆, CrO₂FSbF₆, CrO₂FSb₂F₁₁] were produced. Chromyl fluoride and inorganic salts (CF₃COONa and NaNO₃) produced the following complexes - Na₂CrO₂F₂(CF₃COO)₂ and Na₂CrO₂F₂(NO₃)₂. Unusual solid products were obtained with CrO₂F₂ and NO, NO₂, SO₂.A new method of preparing CrO₂F₂ is also presented.     

Fluordiazadiphosphetidine. 21. Mitt. Die Photochemische Chlorierung von 2,2,2,4,4,4-Hexafluoro-1,3-diethyl (und dipropyl)-1,3,2λ5,4λ5-diazadiphosphetidin und die Herstellung von 2,2,2,4,4,4-Hexafluoro-1-(cyanometyl)-3-methyl-1,3,2λ5,4λ5-diazadiphosphetidin

Summary The result of the chlorination of (CH₃CH₂NPF₃)₂ and (CH₃CH₂CH₂NPF₃)₂ with chlorine under UV-radiation were the new compounds CH₃CH₂(NPF₃)₂CH₂CH₂Cl and CH₃CH₂CH₂(NPF₃)₂CH₂CH₂CH₂Cl. The reaction of CH₃(NPF₃)₂CH₂Cl with KCN and crown-ether gave the new compound CH₃(NPF₃)₂CH₂CN.

     

High-resolution electron microscopy of defects in W4Nb26O77

Several different kinds of planar defects have been observed by means of high-resolution electron microscopy in W₄Nb₂₆O₇₇, such as disordered intergrowth of WNb₁₂O₃₃ and W₃Nb₁₄O₄₄ structural slabs, locally ordered intergrowth with a sequence of AABAAB, two separate microdomains of WNb₁₂O₃₃ and W₃Nb₁₄O₄₄ coexisting with W₄Nb₂₆O₇₇ and a complicated intergrowth of W₄Nb₂₆O₇₇, NNb₂O₅, W₃Nb₁₄O₄₄, and Nb₃₁O₇₇F types of structure.     

From Saturated BN Compounds to Isoelectronic BN/CC Counterparts: An Insight from Computational Perspective

In the present study, the inorganic analogues of alkanes as well as their isoelectronic BN/CC counterparts that bridge the gap between organic and inorganic chemistry are comparatively studied on the grounds of static DFT and Car–Parrinello molecular dynamics simulations. The BN/CC butanes CH₃CH₂BH₂NH₃, BH₃CH₂NH₂CH₃, and NH₃CH₂BH₂CH₃ were considered and compared with their isoelectronic counterparts NH₃BH₂NH₂BH₃ and CH₃CH₂CH₂CH₃. In addition, systematical replacement of the NH₂BH₂ fragment by the isoelectronic CH₂CH₂ moiety is studied in the molecules H₃N(NH₂BH₂)_3–m(CH₂CH₂)_mBH₃ (for m=0, 1, 2, or 3) and H₃N(NH₂BH₂)_2–m(CH₂CH₂)_mBH₃ (for m=0, 1, or 2). The DFT and Car–Parrinello simulations show that the isosteres of the BN/CC butanes CH₃CH₂BH₂NH₃, BH₃CH₂NH₂CH₃, and NH₃CH₂BH₂CH₃ and of larger oligomers of the type (BN)_k(CC)_l where k≥l are stable compounds. The BN/CC butane H₃NCH₂CH₂BH₃ spontaneously produces molecular hydrogen at room temperature. The reaction, prompted by very strong dihydrogen bonding NH???HB, undergoes through the neutral, hypervalent, pentacoordinated boron dihydrogen complex R?BH₂(H₂) [R=(CH₂CH₂)_nNH₂]. The calculations suggest that such intermediate and the other BN/CC butanes CH₃CH₂BH₂NH₃, BH₃CH₂NH₂CH₃, and NH₃CH₂BH₂CH₃ as well as larger BN/CC oligomers are viable experimentally. A simple recipe for the synthesis of CH₃CH₂BH₂NH₃ is proposed. The strength of the dihydrogen bonding appeared to be crucial for the overall stability of the saturated BN/CC derivatives.     

Neue Quecksilber(II)-perjodate

New Mercury(II) Periodates From Hg(NO₃)₂ and H₅IO₆ soluted in nitric acid of variated concentration, the long known Hg₅(IO₆)₂ and the new salts Hg₂HIO₆ (brown), Hg₃(H₂IO₆)₂ (yellow), Hg₃(IO₅)₂ (black), and HgH₃IO₆ (colourless) have been prepared. Dehydration of HgH₃IO₆ leads to the brown salt HgHIO₅. The structure of the new compounds has been deduced from their i.r. spectra. The existence of the earlier reported salts Hg(IO₄)₂, Hg₄I₂O₁₁, Hg₇(IO₇)₂ · 18 H₂O and Hg₆I₂O₁₃ · 20 H₂O has not been confirmed.     

Reactions of transition metal compounds with macrocyclic alkadiynes : IV*. Intramolecular transannular cyclizations with cyclopentadienyldicarbonylrhodium

The macrocyclic alkadiynes, 1,7-cyclododecadiyne, 1,7-cyclotridecadiyne, 1,7- and 1,8-cyclotetradecadiyne, and 1,8-cyclopentadecadiyne react with C₅H₅Rh(CO)₂ in boiling cyclooctane to give pale yellow to white volatile compounds of the compositon C₅H₅Rh(alkadiyne) in which the macrocyclic alkadiyne has undergone an intramolecular transannular cyclization to form a tricyclic cyclobutadiene derivative. The reaction of 1,7-cyclododecadiyne with C₅H₅Rh(CO)₂ also gives a dimer of 1,7-cyclododecadiyne containing a benzene ring. Corresponding reactions of the simple alkynes RCCR (R = C₂H₅ and C₆H₅) with C₅H₅Rh(CO)₂ in boiling cyclooctane failed to give any rhodium—cyclobutadiene derivatives. Instead the reaction of 3-hexyne with C₅H₅Rh(CO)₂ under these conditions gave orange-red (C₅H₅)₂Rh₂(CO)C₄(C₂H₅)₄ and purple-black (C₅H₅)₃Rh₃(CO)(C₂H₅CCC₂H₅) and the reaction of diphenylacetylene with C₅H₅Rh(CO)₂ gave a low yield of the orange complex (C₅H₅)₃Rh₃(C₆H₅CCC₆H₅). The infrared, ¹H NMR, and mass spectra of these new cyclopentadienylrhodium complexes are described.     

Reaktionen von R4Sb2 (R = Me,Et) mit (Me3SiCH2)3M (M = Ga,In) und Kristallstrukturen von [(Me3SiCH2)2InSbMe2]3 und [(Me3SiCH2)2GaOSbEt2]2

Reactions of R₄Sb₂ (R = Me, Et) with (Me₃SiCH₂)₃M (M = Ga, In) and Crystal Structures of [(Me₃SiCH₂)₂InSbMe₂]₃ and [(Me₃SiCH₂)₂GaOSbEt₂]₂ The reaction of (Me₃SiCH₂)₃In with Me₂SbSbMe₂ gives [(Me₃SiCH₂)₂InSbMe₂]₃ ( 1 ) and Me₃SiCH₂SbMe₂. [(Me₃SiCH₂)₂GaOSbEt₂]₂ ( 2 ) is formed by the reaction of (Me₃SiCH₂)₃Ga with Et₂SbSbEt₂ and oxygen. The syntheses and the crystal structures of 1 and 2 are reported.     

The synthesis and structure of triphenylsiloxycyclotriphosphazenes

The triphenylsiloxy-substituted cyclotriphosphazenes, N₃P₃Cl₅OSiPh₃, gem-N₃P₃Cl₄(OSiPh₃)₂, N₃P₃(OSiPh₃)₆, and N₃P₃(OPh)₅OSiPh₃, have been prepared. The synthesis of gem-N₃P₃Cl₄(OSiPh₃)₂ involves the reaction of (NPCl₂)₃ with Ph₃SiONa to form the intermediates gem-N₃P₃Cl₄(OSiPh₃)₂(ONa) and gem-N₃P₃Cl₄(ONa)₂, which yield gem-N₃P₃Cl₄(OSiPh₃)₂ when treated with Ph₃SiCl. The compounds N₃P₃Cl₅OSiPh₃ and N₃P₃(OSiPh₃)₀ are formed by the condensation reactions of N₃P₃Cl₅OBuⁿ and N₃P₃(OBuⁿ)₆, respectively, with Ph₃SiCl. The compound N₃P₃(OPh)₅OSiPh₃ is synthesized by the reaction between N₃P₃(OPh)₅Cl and Et₃SiONa to first give the intermediate N₃P₃(OPh)₅ONa, which yields N₃P₃(OPh)₅OSiPh₃ when reacted with Ph₃SiCl. The structural characterization and properties of these compounds are discussed. The crystal and molecular structure of gem-N₃P₃Cl₄(OSiPh₃)₂ has been investigated by single-crystal X-ray diffraction techniques. The crystals are monoclinic with the space group P2₁/c with a = 16.850(8), b = 12.829(4), c = 18.505(15) Å, and β = 101.00(6)° with V = 3927 ų and Z = 4. © 1996 John Wiley & Sons, Inc.     

Interaction of components in the Cs2HgBr4-Cs2ZnBr4-CsBr ternary system

The interaction of components in the Cs₂HgBr₄-Cs₂ZnBr₄-CsBr ternary system was studied by differential thermal and X-ray powder diffraction analyses. The liquidus surface consists of the crystallization fields of three phases: CsBr, a solid solution of Cs₂HgBr₄ with Cs₂ZnBr₄ (??), and solid solution ?? based on Cs₃ZnBr₅. The ternary eutectic near Cs₂HgBr₄ has the coordinates ??83 mol % Cs₂HgBr₄, 2 mol % Cs₂ZnBr₄, and 15 mol % CsBr and the melting point ??415°C. The triangulating section Cs₂HgBr₄-Cs₃ZnBr₅ is characterized by the eutectic interaction with the eutectic that is degenerate near Cs₂HgBr₄, contains ??3 mol % Cs₃ZnBr₅, and melts at 420°C. This section divides the Cs₂HgBr₄-Cs₂ZnBr₄-CsBr ternary system into two ternary systems Cs₂HgBr₄-CsBr-Cs₃ZnBr₅ and Cs₂HgBr₄-Cs₃ZnBr₅-Cs₂ZnBr₄.     

Zur Kenntnis der Sulfensäurefluoride CF3SF und CF2ClSF sowie deren Dimeren

The Sulfenic Fluorides CF₃SF and CF₂CISF and their Dimers The reactions of R_fSCl (R_f = CF₃, CF₂Cl) with HgF₂ and AgF give R_fSF and the dimer product R_fSF₂SR_f in high yield and various ratios, in contrast, activated KF leads only to R_fSF in low yield. A complex of transition metal and sulfenic halide as an intermediate step is discussed for the dimerisation. As liquid CF₃SF₂SCF₃ disproportionates into CF₃SF₃ and CF₃SSCF₃ and the hydrolysis of CF₃SF₂SCF₃ gives the stable compound CF₃S(O)SCF₃ · PF₃ reacts with R_fSF as well as with R_fSF₂SR_f to R_fSPF₄. The products of the spontaneous decomposition of CF₂ClSF were investigated. I.r., n.m.r., and mass spectra are reported and discussed. It was possible to carry out vapour pressure measurements of CF₂ClSF.     

Reactions of metal carbonyl derivatives : XI. Tertiary phosphine,phosphite and stibine and ditertiaryphosphine and arsine derivatives of bis(μ-phenyl- sulphidotricarbonyliron)

The ditertiary phosphines (C₆H₅)₂P(CH₂)_nP(C₆H₅)₂ (n = 1 and 2), cis(C₆H₅)₂PC₂H₂P(C₆H₅)₂ and (C₆H₅)₂PN(C₂H₅)P(C₆H₅₂ and the ditertiary arsines (C₆H₅)₂As(CH₂)_nAs(C₆H₅)2 (_n = 1 and 2) react with [Fe(CO)₃SC₆H₅]₂ to give a wide range of products, the nature of which depends on the reaction conditions and the ligand involved. Examples of the different types of comp isolated include, (i) Fe₂(CO)₅[(C₆H₅)₂PCH₂P(C₆H₅)₂](SC₆H₅)₂, in which the ligand acts as a monodentate, (ii) {[Fe(CO)₂SC₆H₅]₂[(C₆H₅)₂PC₂H₄P(C₆H₅)₂]}₂, in which two [Fe(CO)₂SC₆H₅]₂ moieties are bridged by two diphosphine ligands, (iii) [Fe(CO)₂SC₆H₅]₂[(C₆H₅)₂PN(C₂H₅)P(C₆H₅)₂], in which the ligand bridges the two iron atoms, and (iv) Fe(CO)₃(SC₆H₅)₂Fe(CO)[(C₆H₅)₂PC₂H₂P(C₆H₅)₂], which contains the ligand chelated to a single iron atom. The tertiary phosphines PR₃ (R=C₂H₅ and C₆H₅), phosphites P(OR′)₃(R′ = CH₃, C₂H₅, i-C₃H₇ and C₆H₅) and the stibine Sb(C₆H₅)₃ bring about mono-, bis- or tris-substitution in [Fe(CO)₃SC₆H₅]₂ depending on the reaction conditions and the ligand involved. Whereas in solution [Fe(CO)₂L(SC₆H₅)]₂ [L = PR₃ (R = C₂H₅ and C₆H₅), P(OC₆H₅)₃ and Sb(C₆H₅)₃] exist as a single isomer, [Fe(CO)₂L′(SC₆H₅)]₂ [L′=P(OR′)₃ (R'=CH₃, C₂H₅ and i-C₃H₇)] occur as a mixture of isomers.