Cp2Zr(C2H4)(PMe3), der erste stabile Ethylenkomplex des Zirkoniums

The complex Cp₂Zr(PMe₃)₂ reacts with ethylene under pressure to give the first ever stable ethylene complex of zirconium, Cp₂Zr(C₂H₄)(PMe₃). Other products of this reaction are the zirconacyclopentane complex, Cp₂Zr(C₄H₈), and polyethylene.     

Cs2[Pr6(C2)]I12 - das erste quaternäre reduzierte Halogenid mit isolierten [M6(C2)]-Clustern

Cs₂[Pr₆(C₂)]I₁₂ — the First Quaternary Reduced Halide with Isolated [M₆(C₂)] Clusters . Cs₂[Pr₆(C₂)]I₁₂ is obtained as one of the major products from the reaction of PrI₃, cesium and carbon in sealed tantalum containers at 850°C. The crystal structure triclinic, P 1 ; a=948.1(2), b=953.6(3), c=1 005.2(3) pm; α=71.01(2); β=84,68(3), γ=89.37(2)°; Z=1 contains discrete Pr₆I₁₂-type clusters elongated along the pseudo-four-fold axis to accommodate the C₂ units (d(C—C)=139 pm). The clusters are connected through common ^i?aI and ^a?iI linkages at metal vertices and edges according to Cs₂[Pr₆(C₂)ⁱI₆^i?aI_6/2]^a?iI_6/2. The cesium cations occupy interstices within the (distorted) iodide layers in a way that “Cs₂I₁₈” dimers are formed, in which Cs⁺ is surrounded by eleven I^?. On the basis of the MO scheme of [Sc₆(C₂]I₁₁, the bonding of the C² unit is discussed and compared with other cluster compounds containing C₂ units.     

Die Reaktion des Rhenium(VII)-oxides mit 1,4-Dioxan Re2O6(μ2-OH)2 · 3 C4H8O2 – ein neues Oxidhydroxid mit Metall-(1,4-Dioxan)-Bindung

Reaction of Rhenium(VII) Oxide with 1,4-Dioxane. Re₂O₆(μ₂-OH)₂ · 3 C₄H₈O₂— a Novel Oxide Hydroxide with Metal-(1,4-Dioxane) Bonds The reaction of Re₂O₇ with 1,4-dioxane in the presence of small amounts of H₂O yields the compound Re₂O₆(OH)₂ · 3(1,4-dioxane). It crystallizes in the triclinic space group P¯1 with a = 10.907(3), b = 12.875(4), c = 7.943(2) Å; α = 108.64(2), β = 103.00(2), γ = 102.29(2)°; Z = 2. The complete X-ray structure analysis (R = 2.9? ) shows the crystals to contain dimeric centrosymmetric Re₂O₆(OH)₂-units with two bridging μ₂-OH groups. The ligand spheres around Re are completed towards distorted octahedra by coordinated 1,4-dioxane molecules (one O donor per Re), the latter linking the dimeric units to endless chains. The rest of the 1,4-dioxane molecules are bonded to the OH-groups through hydrogen bridges and have no contact to Re. Mean bond distances are: Re? O(bridge) 2.065 (2.059…2.070(4)) Å, Re? O(1,4-dioxane) 2.478 (2.469 and 2.486(5)) Å, Re? O (terminal) 1.707 (1.694…1.720(5)) Å.     

Unithiol (2,3-Dimercaptopropansulfonat Natriumsalz) (I), das mit einer Reihe zweiwertiger Schwermetallionen stabile Chelate bildet

Ohne Zusammenfassung     

Na5FeS4 – das erste Thioferrat(III) mit diskreten tetraedrischen Anionen

Na₅FeS₄ — the First Thioferrate(III) with Discrete Tetrahedral Anions Ruby red crystals of Na₅FeS₄ were obtained by reacting a stoichiometric mixture of Na₂S, Fe, and S at 970 K. The compound is orthorhombic, space group Pbca, with a = 11.947(5), b = 7.091(3), c = 21.54(1) Å, Z = 8. The crystal structure was determined from single crystal diffractometer data. The atomic arrangement – which corresponds to that of Na₅GaO₄ [1] – is characterized by discrete tetrahedral [FeS₄] groups, separated from each other by Na⁺ cations. Measurements of the magnetic susceptibilities show coupling effects between Fe³⁺ ions below 28 K. At higher temperatures a Curie-Weiss behaviour indicates a high-spin-state of the Fe³⁺ ions. Relationships between the interatomic distances and the magnetic moments in alkali thioferrates are discussed.     

Beiträge zur Chemie des Phosphors. 142. P6(t-Bu)5H – das erste Cyclotetraphosphan mit P2-Seitenkette

Contributions to the Chemistry of Phosphorus. 142. P₆(t-Bu)₅H – the First Cyclotetraphosphane with a P₂ Side Chain The thermolysis of 1, 2-di-tert-butyldiphosphane, H(t-Bu)P? P(t-Bu)H, leads to formation of the hitherto unknown hexaphosphane P₆(t-Bu)₅H ( 1 ). In the first instance the iso-P₅H₅ derivative P₅(t-Bu)₄H [3] is formed, which reacts further with H₂(t-BuP)₂ or H₂(t-BuP)₃ yielding 1 . Compound 1 has been isolated in the pure state and structurally characterized as 1-(1,2-di-tert-butyldiphosphino)-2, 3, 4-tri-tert-butyl-cyclotetraphosphane, i. e. as a four-membered ring compound with a P₂ side chain. Due to the chirality of the P atoms in the side chain, 1 exists as a mixture of two configurational isomers, the threo-and the erythro-form.     

Das erste Erdalkalimetall-Argentato-Mercurat(II): BaAg2Hg2O4

Summary BaAg₂Hg₂O₄ was prepared by an oxygen high-pressure technique. Single crystal X-ray investigations led to tetragonal symmetry, space group D _4h ³ – P4/nbm;a=6.793;c=7.086 Å;Z=2. Hg²⁺ and Ag⁺ show dumb-bell like coordination by oxygen whereas Ba²⁺ ions are surrounded by 8 O^2– forming distorted cubes. The BaO₈-polyhedra distortions are discussed in respect to the incorporation of Hg²⁺ ions into the BaAg₂O ₄ ^2– network.