Über eine bequeme Darstellung von 1, 4-Dioxy-n-butan (Tetramethylenglykol) und 1, 4-Dibrom-n-butan

Ohne Zusammenfassung     

α- und β-BaCu2X2 (X ≙ S,Se) – Darstellung von Einkristallen in Kaliumchalkogenocyanat-Schmelzen

α- and β-BaCu₂X₂ (X ≙ S, Se) – Preparation of Single Crystals in Potassium Chalcogenocyanate Fluxes α- and β-BaCu₂S₂, as well as the isotypic selenides, could be obtained in a flux of potassiumthio- or potassiumselenocyanate at 480 °C, respectively. Up to now only the preparation of the golden yellow α-BaCu₂S₂ compound in the form of some crystals is reported [1]. Single crystal four-circle diffractometer data confirm the already known structure of α-BaCu₂S₂ and α-BaCu₂Se₂, and the expected BaZn₂P₂ structure type for the β-modification of the two chalcogenides. β-BaCu₂Se₂ could be prepared for the first time. α-BaCu₂S₂ transforms irreversibly at 540 (±10) °C into the β-modification. The structural relationship between the two structure types is described. α-BaCu₂S₂ is diamagnetic, β-BaCu₂S₂, on the other hand, shows a small, temperature-independent paramagnetism.     

Über Ferrocen-Acetylene, 4. Mitt.: Darstellung und Lichtabsorption von Ferrocenyl-thiophenen und Derivaten des Ferrocenyl-acetylens

Zusammenfassung 2-Ferrocenyl-thiophene wurden aus Ferrocenyl-diacetylenen durch Cyclisierung mit H₂S dargestellt.Durch eine intramolekulareWittig-Reaktion war Ferrocenyl-propiolsäureester und daraus der entsprechende Acetylenalkohol (Fc–CC–CH₂OH) und-aldehyd (Fc–CC–CHO) zugänglich. Di-ferrocenyl-propinon (X) und-penteninon (XIV) wurden über das Li-Derivat von Ferrocenyl-acetylen erhalten.Die UV-Spektren der Ferrocenyl-thiophene und-acetylene werden diskutiert.

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2-Ferrocenyl-thiophenes have been prepared from ferrocenyl-diacetylenes by cyclization with H₂S.By means of an intramolecularWittig reaction ethyl ferrocenyl propiolate was obtained and subsequently converted into the corresponding alcohol (Fc–CC–CH₂OH) and aldehyde (Fc–CC–CHO).Diferrocenyl-propynone (X) and diferrocenyl-pentenynone (XIV) have been obtained via lithium ferrocenylacetylide.The ultraviolet spectra of the ferrocenyl-thiophenes and ferrocenyl-acetylenes are reported and briefly discussed.

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Herrn Prof. Dr.H. Bretschneider zum 60. Geburtstag gewidmet.

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3. Mitt.:K. Schlögl undH. Egger, Mh. Chem.94, 376 (1963).

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22. Mitt.:H. Egger undK. Schlögl, J. Organomet. Chem.2, 398 (1964).     

Darstellung und kristallstruktur von μ3-allyl-μ1-chlorobis(triphenylphosphin)dipalladium(I)

μ₃-Allyl-μ₁-chloro-bis(triphenylphosphine)dipalladium(I) was obtained by the reaction of (π-C₃H₅PdCl)₂ with P(C₆H₅)₃ and NaOCH₃. The X-ray structure analysis of the yellow air-stable crystals confirms the presence of a PdPd bond (2.623 Å) and a bridging μ₃-allyl group. The PdC distances to the terminal carbon atoms of the allyl group are 2.07(1) Å. The distances of the Pd atoms to the bridging chloride ion are 2.433(3) and 2.438(3) Å.     

α-Keggin tungstogermanate-supported transition metal complexes: hydrothermal synthesis,characterization, and magnetism of Cu2(phen)4(GeW12O40) and [Ni2(bpy)4(H2O)2(GeW12O40)]⋅2H2O

Two new α-Keggin polyoxometalates, [Cu₂(phen)₄(GeW₁₂O₄₀)] (1) and [Ni₂(bpy)₄(H₂O)₂(GeW₁₂O₄₀)]·2H₂O (2) (phen?=?1,10-phenanthroline, bpy?=?2,2′-bipyridine), have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, single-crystal X-ray diffraction, and magnetic properties. Compound 1 crystallizes in the monoclinic system, space group P2(1)/c, and 1 is assembled into two-dimensional (2-D) layers parallel to (1?0?1) based on the adjacent phen π···π stacking interactions (3.788(8)?Å). Variable temperature magnetic measurements show ferromagnetic behavior from 300 to 2?K. Compound 2 crystallizes in the triclinic system, space group P-1, and 2 is assembled into 2-D layers parallel to (1?0?1) based on the adjacent bpy π···π stacking interactions (3.07?Å). Variable temperature magnetic measurements show a weak ferromagnetic behavior from 300 to 26?K followed by antiferromagnetic behavior below 26?K.     

Synthesis,Spectroscopic Properties and Crystal Structure of (C4N2H12)2Zr(C2O4)4·H2O

The title compound (C4N2H12)2Zr(C2O4)4·H2O 1 was synthesized by the reaction of ZrOCl2·8H2O, H2C2O4·2H2O and piperazinium in aqueous solution. Single-crystal X-ray analysis has revealed that compound 1 (C16H26N4O17Zr, Mr = 637.63) crystallizes in the monoclinic system, space group P21/c with a = 9.0425(3), b = 13.3844(3), c = 19.1191(5)A, β = 98.365(1)o, V = 2289.34(11) A3, Z = 4, Dc = 1.850 g/cm3, F(000) = 1304, μ = 0.577 mm-1, the final R = 0.0240 and wR = 0.0628 for 4386 observed reflections with I > 2σ(I). X-ray crystal-structure analysis suggests that compound 1 consists of [Zr(C2O4)4]4- anion and two protonated piperazinium cations. The anions are linked through hydrogen bonds of piperazinium. FT-IR and Raman spectra clearly show the existence of oxalate groups in the crystal lattice.     

Single-molecule magnetism behavior of [Mn12O12(O2CR)16(H2O)4]2− salts

(PPh₄)₂[Mn₁₂O₁₂(O₂CCHCl₂)₁₆(H₂O)₄] (3) has been prepared by the two-electron reduction of [Mn₁₂O₁₂(O₂CCHCl₂)₁₆(H₂O)₄] (2) using iodide. Crystallization from CH₂Cl₂/hexanes yields a mixture of two crystal forms, 3·4CH₂Cl₂·H₂O (3a) and 36CH₂Cl₂ (3b), which are triclinic and monoclinic, respectively. They are both trapped valence 2Mn(II), 6Mn(III), 4Mn(IV). DC magnetization data for dried, unsolvated 3 in 1.80–4.00 K and 10–70 kG ranges were fit to give S=10, D=−0.28 cm⁻¹, g=2.00. Frequency-dependent out-of-phase (χ″_M) signals in AC susceptibility studies on crystalline sample of 3a and 3b combined with DC relaxation decay data were fit to the Arrhenius equation to give an effective energy barrier of U_eff=18.5 and 30.3 K, respectively. Magnetization vs. DC field sweeps on single crystals of 3a and 3b gave hysteresis loops containing steps due to quantum tunneling of magnetization (QTM). The step separations yielded ∣D∣/g values of 0.087 and 0.14 cm⁻¹, and consequently U=20 and 39 K (for g=2) for 3a and 3b, respectively, suggesting that the differences in U_eff are primarily caused by changes to D. This work demonstrates the sensitivity of the magnetic properties of [Mn₁₂]²⁻ single-molecule magnets to subtle differences in their environment.     

Über die Darstellung von Derivaten des 3-Amino-8-hydroxy-chinazolons-(4)

Zusammenfassung 3-Hydroxy- und 3-Methoxy-anthranilsäure werden verestert, die Ester acyliert und die entstehenden Acylaminoester mit Hydrazin in 2-substituierte 8-Hydroxy- bzw. 8-Methoxy-3-amino-chinazolone-(4) übergeführt. Durch Umsetzung von Alkyl- und Acylisothiocyanaten mit Aminochinazolonen wirden neue Thioharnstoffe erhalten.     

Darstellung und reaktivität von zweikernigen pentamethylcyclopentadienyloxomolybdänsulfiden

Reaction of Cp^*₂Mo₂S₄ (Cp^*  η⁵C₅Me₅) with oxygen yields two isomers of Cp^*₂Mo₂OS₃ and Cp^*₂Mo₂O₂S₂, the constitution of which is determined by means of IR, ¹H and ⁹⁵Mo NMR spectroscopy as well as by X-ray diffraction analysis. The sulfur liberated in this reaction is oxidized and incorporated into an unusually coordinated μ,η¹-thiosulfate ligand of the compound [Cp^*₂Mo₂(μ,η²-S₂)(μ-S)(υ,η¹-S₂O₃)]. The reaction of all of these compounds with (CO)₅Cr(THF) and (CH₃CN)₃Cr(CO)₃, respectively, gives clusters either containing a trigonal-bipyramidal Mo₂CrS₂ or a cubane-like Mo₂Cr₂O_nS_4-n skeleton (n = 1,2) with five metal-metal bonds. This reaction enables the straightforward incorporation of oxygen atoms into 62-e heterocubane clusters and thus the investigation of ⁹⁵Mo chemical shifts of mixed oxo/thio-heterocubanes by means of NMR spectroscopy.     

Synthese und Reactivität von (2,6-iPr2Ph-dad)Ni(C2F4)

Upon warming the reaction mixture of Ni(cdt), C₂F₄, and 2,6-ⁱPr₂Ph-dad in THF from −78°C to room temperature the red-violet complex (2,6-ⁱPr₂Ph-dad)Ni(C₂F₄) (1) is obtained. 1 reacts with ethene already at −78°C by coupling of the olefinic ligands with the nickel atom to form the blue nickelatetrafluoro-cyclopentane compound (2,6-ⁱPr₂Ph-dad)Ni(C₂H₄C₂F₄) (2).     

Untersuchungen über Aluminiumhydroxyde und -oxyde, 2. Mitt.: Darstellung von Reinst-Aluminiumhydroxyden durch Hydrolyse

Zusammenfassung Mit Hilfe der Hydrolyse von organischen Aluminium-verbindungen gelangt man zu sehr reinen und definierten Aluminiumhydroxyden. Besonders das Aluminiumäthylat eignet sich zur Herstellung eines Bayerits, der infolge seiner Reinheit und seines guten Kristallisationszustandes als Standardmaterial für spätere Abbau-Versuche geeignet ist.Mit 2 Abbildungen     

Über die Darstellung von m-Hydroxybenzylaminen und m-Hydroxybenzaldehyden aus Chinolacetaten

Zusammenfassung Es wird an einigen Beispielen die leichte Zugänglichkeit von m-Hydroxybenzylaminen und m-Hydroxybenzaldehyden aus m-Hydroxybenzonitrilen aufgezeigt. Letztere Verbindungen sind aus Chinolacetaten durch Addition von Cyanid-Ion unter gleichzeitiger Abspaltung von Essigsäure leicht und in guten Ausbeuten zugänglich.Dem Präsidenten der Max-Planck-Gesellschaft, Prof. Dr. Dr. h. c. mult.Adolf Butenandt, in Verehrung zum 60. Geburtstag gewidmet.     

Acetate-Functionalized Zirconium-Substituted Tungstogermanate, [Zr4O2(OH)2(CH3COO)2(α-GeW10O37)2]12−

The two acetate-functionalized zirconium(IV)-substituted tungstogermanates, Na₈K₄[Zr₄O₂(OH)₂(CH₃COO)₂(α-GeW₁₀O₃₇)₂] · 33H₂O and Na₈Cs₄[Zr₄O₂(OH)₂(CH₃COO)₂(α-GeW₁₀O₃₇)₂] · 32H₂O, were synthesized by the reaction of ZrOCl₂ with [A-α-GeW₉O₃₄]¹⁰⁻ in pH = 4.8 buffer and their structures were determined by single-crystal X-ray analysis. Both of them contain a centrosymmetric polyanion [Zr₄O₂(OH)₂(CH₃COO)₂(α-GeW₁₀O₃₇)₂]¹²⁻ consisting of two {α-GeW₁₀O₃₇} units sandwiching an inorganic–organic hybrid {Zr₄O₂(OH)₂(CH₃COO)₂} cluster. The polyanion contains a mixing of seven- and eight-coordinate Zr centres. The two compounds were also characterized by elemental analysis, IR spectroscopy, UV–vis and TG–DSC analysis.     

New 1D and 2D metal oxygen connectivities in Cu(II) succinato and glutarato coordination polymers: [Cu3(H2O)2(OH)2(C4H4O4)2] · 4H2O, [Cu4(H2O)2(OH)4(C4H4O4)2] · 5H2O and [Cu5(OH)6(C5H6O4)2] · 4H2O

Two Cu(II) hydroxo succinates [Cu₃(H₂O)₂(OH)₂(C₄H₄O₄)₂]?·?4H₂O (1) and [Cu₄(H₂O)₂(OH)₄(C₄H₄O₄)₂]?·?5H₂O (2) and one Cu(II) hydroxo glutarate [Cu₅(OH)₆(C₅H₆O₄)₂]?·?4H₂O (3) have been prepared and structurally characterized by single crystal X-ray diffraction methods. They feature 1D and 2D copper oxygen connectivity of elongated {CuO₆} octahedra in “4?+?1?+?1” and “4?+?2” coordination geometries. Within 1, linear trimers of three edge-sharing {CuO₆} octahedra are connected into copper oxygen chains, which are bridged by the anti conformational succinate anions to generate 2D layers with mono terminally coordinating gauche succinate anions on both sides. The layers are assembled into a 3D framework by interlayer hydrogen bonds with lattice H₂O molecules distributed in channels. Different from 1, the principal building units in 2 are linear tetramers of four edge-sharing {CuO₆} octahedra. The tetramers are condensed into copper oxygen chains and the succinate anions interlink them into a 3D framework with triangular channels filled by lattice H₂O molecules. The {CuO₆} octahedra in 3 are edge-shared to form unprecedented 2D inorganic layers with mono terminally coordinating glutarate anions on both sides. Interlayer hydrogen bonding interactions are responsible for supramolecular assembly of the layers into a 3D framework with lattice H₂O molecules in the channels. The inorganic layers in 3 can be described as hexagonal close packing of oxygen atoms with the Cu atoms in the octahedral cavities. The title compounds were further characterized by elemental analyses, IR spectra and thermal analyses.     

Über Ferrocen-Acetylene, 2. Mitt.: Darstellung und Reaktionen von Ferrocenyl-alkinen und-alkinyl-ketonen (11. Mitt. über Ferrocenderivate)

Zusammenfassung Ausgehend von Ferrocenyl-acetylen-carbinolen und-glykolen wurden neue ungesättigte Ferrocenderivate dargestellt.So liefert partielle Reduktion Alkenyl-carbinole, von denen Ferrocenyl-styryl-carbinol in der cis- und trans-Konfiguration erhalten werden konnte. Reduktion mit LiAlH₄/AlCl₃ führt zu Mono- und Diferrocenyl-alkinen, deren -CH₂-Gruppe schon an der Luft, noch glatter aber mit MnO₂ zu CO oxydiert wird. Durch MnO₂-Oxydation wurden aus sekundären Ferrocenyl-alkinyl- und-alkenyl-carbinolen (und-glykolen) die entsprechenden—präparativ interessanten—Mono- und Diketone leicht zugänglich. Aus Ferrocenyl-äthinyl-keton z. B. können Heterocyclen erhalten werden. Diferrocenyl- und Phenyl-ferrocenyl-butadien wurden dargestellt und ihre UV-Absorption mit dem Spektrum der Diphenyl-verbindung verglichen. Versuche zur Synthese höher ungesättigter Systeme (Hexatrien und Kumulene) ergaben noch keine eindeutigen Ergebnisse.Basen- und säurekatalysierte Umlagerungen geeigneter ungesättigter Ferrocenderivate führten u. a. zur Darstellung von Ferrocenyl-allen und Ferrocenyl-phenyl-allen sowie von Ferrocenylacrolein.Mit 3 Abbildungen1. Mitt.:K. Schlögl undA. Mohar, Mh. Chem.92, 219 (1961).10. Mitt.:K. Schlögl undM. Peterlik, Tetrahedron Lett., im Druck     

Über die Darstellung von S2O5F2 aus Fluorsulfonsäure

Zusammenfassung Während die Umsetzung von HSO₃F mit P₂O₅ zu POF₃ führt, kann die Reaktion mit As₂O₅ AsF₅ oder ein flüchtiges Arsenfluoridfluosulfonat ergeben, welches sich zu Pyrosulfuryl-fluorid zersetzen läßt. S₂O₅F₂ ist thermisch in Glas bis über 300° stabil.Herrn Prof. Dr.A. Klemenc zum 70. Geburtstag gewidmet.