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  • Rhenium  (6)
  • preparation  (4)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 596 (1991), S. 89-92 
    ISSN: 0044-2313
    Keywords: Calcium oxychloride ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: An Oxychloride of Calcium: Ca4OCl6Ca4OCl6 (hexagonal, P63mc, Z = 2), a = 905.8(3), c = 686.3(4) pm, (R = 0.031) crystallizes as colourless needles from reducing melts (CaCl2, Ca) that contain small amounts of „oxygen“. It contains „isolated“ tetrahedral units [Ca4O] and is isotypic with e.g., Ba4OCl6, Yb4OCl6 and K6HgS4. Ca4OCl6 does not form in the dehydration process of, for example, CaCl2 · 6 H2O.
    Notes: Ca4OCl6 (hexagonal, P63mc, Z = 2, a = 905.8(3)); c = 686.3(4) pm, (R = 0,031) kristallisiert in Form farbloser Nadeln aus „reduzierenden Schmelzen“ (CaCl2, Ca), die wenig „Sauerstoff“ enthalten. Es enthält „isolierte“ tetraedrische [Ca4O]-Einheiten und ist isotyp mit z. B. Ba4OCl6, Yb4OCl6 oder K6HgS4. Ca4OCl6 entsteht nicht beim Entwässern von z. B. CaCl2 · 6 H2O.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 604 (1991), S. 7-15 
    ISSN: 0044-2313
    Keywords: Rhenium ; crystal structure ; thermolysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: (NH4)3[Re3Cl12]: Synthesis, Crystal Structure, and Thermolysis(NH4)3[Re3Cl12] may be obtained by reaction of ReCl3 with liquid ammonia and subsequent reaction of the solid product with hydrochloric acid solution or, less pure, directly from ReCl3 and NH4Cl in hydrochloric acid. The crystal structure (monoclinic, P21/m, Z = 2, a = 946.82(6), b = 1138.37(6), c = 912.30(4)pm, β = 93.840(5)°) contains the isolated building units [Re3Cl12]3-. The anions are connected via the NH4+ cations (symbolized by N1 and N2) that have coordination numbers of 10(N1) and 9(N2). Thermal decomposition was investigated by simultaneous DSC/TG-MS measurements. It leads, finally, to metallic rhenium and the gases HCL and N2, but consists of three steps at 320, 420 and 480°C, respectively, with (NH4)2[ReCl6] and ReCl3 as intermediate products.
    Notes: Bisher unbekanntes (NH4)3[Re3Cl12] erhält man durch Behandeln von ReCl3 mit fl. NH3 und anschließender Umsetzung des Reaktionsproduktes mit Salzsäure oder, weniger rein, direkt aus ReCl3 und NH4Cl in Salzsäure. In der Kristallstruktur (monoklin, P21/m, Z = 2; a = 946,82(6); b = 1138,37(6); c = 912,30(4) pm; β = 93,840(5)°) liegen isolierte Baueinheiten [Re3Cl12]3- vor. Die Anionen werden durch die Kationen NH4+ (repräsentiert durch N1 und N2) miteinander verknüpft, sie weisen Koordinationszahlen von 10 (N1) bzw. 9 (N2) auf. Der thermische Abbau wurde mittels simultaner DSC/TG-MS untersucht. Er führt letztlich zu metallischem Rhenium und den Gasen HCl und N2 und erfolgt in drei Stufen bei 320, 420 und 480°C, wobei als Zwischenprodukte (NH4)2[ReCl6] und ReCl3 auftreten.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 604 (1991), S. 17-26 
    ISSN: 0044-2313
    Keywords: Rhenium ; crystal structure ; syntheses ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structures of Methyl-Substituted Ammonium-μ-trichloro-nonachloro-trirhenates(III), (NH4-xMex)3[Re3Cl12] (1 ≤ x ≤ 3)The chlorides (NH3Me)3[Re3Cl12] (1), (NH2Me2)3[Re3Cl12] (2) and (NHMe3)3[Re3Cl12] (3) are obtained from the binary components, for example (NH3Me)Cl and ReCl3, by slow evaporation of the hydrochloric-acid solutions as brick red single crystals. The crystal structures were determined from four-circle diffractometer data.1:orthorhombic, Pnma, Z = 4; a = 1667.93(9); b = 1197.01(5); c = 1110.44(5) pm; R = 0,115; Rw = 0,062.2:monoklin, P21/n, Z = 4; a = 1563,03(12); b = 1648,73(10); c = 984,34(7) pm; β = 93,422(8)°; R = 0,054; Rw = 0,035.3:monoklin, P21/n, Z = 4; a = 1651,7; b = 1679,5; c = 1014,2pm; β = 90,3°; R = 0,107; Rw = 0,075.
    Notes: Die Chloride (NH3Me)3[Re3Cl12] (1), (NH2Me2)3[Re3Cl12] (2) und (NHMe3)3 [Re3Cl12] (3) erhält man aus den binären Komponenten, z. B. (NH3Me)Cl und ReCl3, beim langsamen Eindunsten der salzsauren Lösungen als ziegelrote Einkristalle. Die Kristallstrukturen wurden aus Vierkreis-Diffraktometer-Daten bestimmt.1:orthorhombisch, Pnma, Z = 4; a = 1667,93(9); b = 1197,01(5); c = 1110,44(5)pm; R = 0,115; Rw = 0,062.2:monoklin, P21/n, Z = 4; a = 1563,03(12); b = 1648,73(10); c = 984,34(7)pm; β = 93,422(8)°; R = 0,054; Rw = 0,035.3:monoklin, P21/n, Z = 4; a = 1651,7; b = 1679,5; c = 1014,2pm; β = 90,3°; R = 0,107; Rw = 0,075.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 604 (1991), S. 27-33 
    ISSN: 0044-2313
    Keywords: Rhenium ; crystal structure ; ir, nmr spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: (NMe4)[Re3Cl10(H2O)2] · 2H2O  -  not a 5/3-Hydrate according to [Re3Cl9(H2O)3] · 2H2ONew investigations of the so-called 5/3-hydrate, “[Re3Cl9(H2O)3] · 2H2O”, revealed that it is in fact (NMe4)[Re3Cl10(H2O)2] · 2HO. Low temperature (173 K) single crystal diffractometry confirms the main features of the previously determined crystal structure (hexagonal, P62c, No. 190; a = 937.3(2), c = 1461.2(3) pm; z = 2; Vm = 334.8 cm3/mol; R = 0.030, Rw = 0.022). There are, however, two important differences. First, the channels in the [00.1] direction contain cations NMe4+.These are disordered in a way that their orientation is “up and down” parallel to [00.1]. Infrared and solid-state 13C-NMR spectra confirm the appearance of the NMe4+ cation. Secondly, the in plane, terminal (i, t) positions at the Re3 triangle are not occupied by H2O ligands alone. Rather, the anion [Re3Cl10(H2O)2]- occurs, with statistical distribution of two water molecules (dRe—o = 224(2) pm) and one chloride ion (dRe—cl = 248(1) pm) over the three i,t positions.
    Notes: Neue Untersuchungen an dem als 5/3-Hydrat beschriebenen „[Re3Cl9(H2O)3] · 2H2O“ ergaben, daß es sich hierbei um (NMe4) [Re3Cl10(H2O)2] · 2H2O handelt. Tieftemperaturmessungen (173 K) am Einkristall bestätigen weitgehend die früher bestimmte Kristallstruktur (hexagonal. P62c, Nr. 190; a = 937,3(2), c = 1461,2(3) pm; Z = 2; Vm = 334,8 cm3/mol; R = 0,030; Rw = 0,022). Es bestehen jedoch zwei wichtige Unterschiede: In den Kanälen längs [00.1] befinden sich die Kationen NMe4+; sie sind derart fehlgeordnet, daß die Spitzen der Tetraeder in und gegen Richtung [00.1] orientiert sind. IR- und Festkörper-13C-NMR-Spektrum sind im Einklang mit der Erwartung für das Kation NMe4+. Die in plane, terminal-(i,t)-Positionen am Re3-Ring sind nicht mit drei Wassermolekülen besetzt: Es liegt vielmehr die Baugruppe [Re3Cl10(H2O)2]- vor, mit statistischer Verteilung von zwei Koordinationswasser (dRe—o = 224(2)pm) und einem Chlorid-Ion (dRe—cl = 248(1) pm) auf den drei i,t-Positionen.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1655-1660 
    ISSN: 0044-2313
    Keywords: Rhenium ; Crystal Structure ; Hydrogen Bonding ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal Structure of (NMe4)2[Re3Br11(H2O)] [Re3Br9(H2O)3](H2O)2.(NMe4)2[Re3Br11(H2O)] [Re3Br9(H2O)3](H2O)2 crystallizes from hydrobromic acid solution of Re3Br9 · 2 H2O and NMe4Br at 0 - 5°C. The crystal structure (monoclinic; P21/m (Nr. 11); a = 967.9(3); b = 1 529.7(4); c = 1 710.9(4) pm; β = 91.66(2)°; Z = 2; R = 0.113; Rw = 0.068) has been determined from four-circle diffractometer data. The structure contains two different cluster units of trivalent rhenium, isolated anionic [Re3Br11(H2O)]2- units and neutral cluster units that are connected through crystal water molecules to chains∞1{[Re3Br9(H2O)3](H2O)2}.
    Notes: (NMe4)2[Re3Br11(H2O)] [Re3Br9(H2O)3](H2O)2 kristallisiert aus einer bromwasserstoffsauren Lösung von Re3Br9 · 2 H2O und NMe4Br als dunkel-rotbraune Einkristalle bei 0 - 5°C aus. Die Kristallstruktur wurde aus Vierkreis-Diffraktometerdaten bestimmt: monoklin; P21/m (Nr. 11); a = 967,9(3); b = 1 529,7(4); c = 1 710,9(4) pm; β = 91,66(2)°; Z = 2; R = 0,113; Rw = 0,068. In der Struktur liegen zwei unterschiedliche Clustereinheiten vor: Eine anionische, isolierte Baueinheit, [Re3Br11(H2O)]2-, sowie eine neutrale über Kristallwasser zu Strängen gemäß ∞1{[Re3Br9(H2O)3](H2O)2} verknüpfte Einheit.
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  • 6
    ISSN: 0044-2313
    Keywords: Rhenium ; rubidium rhenium halide hydrates ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: [Rb2(H2O)2][Re3(μ-Cl)3Br7(H2O)2]2 · H2O, a Mixed Halide-Hydrate with the Anionic Dimer {[Re3(μ-Cl)3Br7(H2O)2]2 · H2O}2-[Rb2(H2O)2][Re3(μ-Cl)3Br7(H2O)2]2 · H2O crystallizes as dark redbrown single crystals from an hydrobromic-acid solution of ReCl3 and RbBr at 0°C. An important feature of the crystal structure (monoclinic, C2/c; a = 1494.61(8); b = 835.71(4); c = 3079.96(19) pm; β = 97.801(4)°; Vm = 573.9(4) cm3mol-1; R = 0.060; Rw = 0.038) is the connection of two anions [Re3(μ-Cl)3Br7(H2O)2]- via a water molecule to dimers, {[Re3(μ-Cl)3Br7(H2O)2]2 · H2O}2-. These dimeric units are contained in slabs that are stacked in the [001] direction and held together by Rb+ cations and crystal water.
    Notes: [Rb2(H2O)2][Re3(μ-Cl)3Br7(H2O)2]2 · H2O kristallisiert in dunklen, rotbraunen Einkristallen aus bromwasserstoffsaurer Lösung von Rheniumtrichlorid und Rubidiumbromid bei 0°C. Ein wichtiges Merkmal der Kristallstruktur (monoklin; C2/c; a = 1494,61(8); b = 835,71(4); c = 3079,96(19) pm; β = 97,801(4)°; Vm = 573,9(4) cm3mol-1; R = 0,060; Rw = 0,038) ist die Verknüpfung zweier Anionen [Re3(μ-Cl)3Br7(H2O)2]- über ein Wassermolekül zu Dimeren {[Re3(μ-Cl)3Br7(H2O)2]2 · H2O}2-. Diese dimeren Baugruppen sind zu Schichtpaketen zusammengefaßt, die längs [001] gestapelt und über die Rb+-Ionen in Gemeinsamkeit mit Kristallwasser verbunden sind.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 602 (1991), S. 31-37 
    ISSN: 0044-2313
    Keywords: Alkali-iodoindates(III) ; indium ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structures of the Alkali-tetraiodoindates(III), AInI4 (A = Li, K, Rb, Cs)Single crystals of the yellow alkaliiodoindates(III), AInI4 (A = Li, K, Rb, Cs), are obtained from mixtures of the binary components by slow cooling of the melts. LiInI4 is isotypic with LiAlCl4: monoclinic, P21/c, Z = 4; a = 838.9(4); b = 751.2(3); c = 1526,7(8) pm; β = 92.67(4)°. KInI4 belongs to the ATIX4 type of structure (A = NH4, K, Rb; X = Br, I): cubic, F4 3c, Z = 24; a = 1990.8(1) pm. RbInI4 crystallizes with the β-GaBr2 type: trigonal, R3c, Z = 18; a = 2452.6(6); c = 978.6(4) pm. CsInI4 is isostructural with CsTII4: monoclinic, P21/c, Z = 4; a = 738.4(1); b = 1875.7(3); c = 853.6(2) pm; β = 105.75(2)°. In all structures almost regular tetrahedral polyhedra [InI4]- occur. The coordination numbers of the alkali cations cover the wide range from 6 (Li+) via 9 (Rb+) and 11 (Cs+) to 12 (K1+).
    Notes: Einkristalle der gelben Iodoindate(III) der Alkalimetalle, AInI4 (A = Li, K, Rb, Cs), erhält man aus Gemengen der binären Komponenten durch langsames Abkühlen der Schmelzen. LiInI4 ist isotyp mit LiAlCl4: monoklin, P21/c, Z = 4; a = 838,9(4); b = 751,2(3); c = 1526,7(8) pm; β = 92,67(4)°. KInI4 gehört zum ATIX4-Typ (A= NH4, K, Rb; X= Br, I): kubisch, F4 3c, Z = 24; a = 1990,8(1) pm. RbInI4 kristallisiert im β-Ga[GaBr4]-Typ: trigonal, R3c, Z = 18; a = 2452,6(6); c = 978,6(4) pm. CsInI4 ist isotyp mit CsTII4: monoklin, P21/c, Z = 4; a = 738,4(1); b = 1875,7(3); c = 853,6(2) pm; β = 105,75(2)°. Stets liegen annähernd tetraedrische Baugruppen [InI4]- vor. Die Koordinationszahlen der Alkali-Kationen überstreichen das Spektrum von 6 (Li+) über 9 Rb+, 11 (Cs+) bis 12 (K1+).
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 695-698 
    ISSN: 0044-2313
    Keywords: Rhenium ; crystal structure ; hydrogen-bonding ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A Chloroacid of Trivalent Rhenium: Hydroxonium Decachloro Diaqua Trirhenate(III) Pentahydrate, H3O[Re3Cl10(H2O)2] · 5H2O.A chloroacid of rhenium(III), H3O[Re3Cl10(H2O)2] · 5H2O, was obtained at room temperature from a saturated solution of “ReCl3 · 2H2O” with an excess of NaCl in concentrated hydrochloric acid. The crystal structure (tetragonal, P41212 (Nr. 92); a = 1 150.9(2) pm; c = 1 592.2(6) pm; Z = 4; R = 0.086; Rw = 0.066) has been determined from four-circle diffractometer data. The structure contains isolated cluster anions, [Re3Cl3i,bCl6o,tCli,t (H2O)2i,t]-, which are enclosed by a cage of water molecules. These building units are connected with each other through a “strong” hydrogen-bonding system.
    Notes: Die Chlorosäure H3O[Re3Cl10(H2O)2] · 5H2O kristallisiert aus einer mit NaCl und „ReCl3 · 2H2O“ gesättigten Lösung in konz. Salzsäure bei Raumtemperatur aus. Die Kristallstruktur wurde aus Vierkreis-Diffraktometerdaten bestimmt: tetragonal, P41212 (Nr. 92); a = 1 150,9(2) pm; c = 1 592,2(6) pm; Z = 4; R = 0,086; Rw = 0,066. In der Struktur liegen isolierte, anionische, trimere Einheiten [Re3Cl3i,bCl6o,tCli,t(H2O)2i,t]- vor, welche über „starke“ Wasserstoffbrückenbindungen „käfigartig“ mit Wassermolekülen umgeben und durch diese Hydrathülle miteinander vernetzt sind.
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  • 9
    ISSN: 0044-2313
    Keywords: Alkali uranium halides, A2UX5 (A = K, Rb; X = Cl, Br, I) ; preparation ; crystal structure ; magnetic susceptibility ; UV-Vis spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese, Kristallstruktur, Magnetismus und Absorptionsspektren von Halogeniden des Typs A2UX5 (A = K, Rb; X = Cl, Br, I)Die ternären Uran(III)-halogenide A2UX5 (A = K, Rb; X = Cl, Br, I) wurden aus den binären Komponenten AX und UX3 in verschweißten Tantalampullen gewonnen. Nach Guinier-Aufnahmen (Raumtemperatur) kristallisieren sie sämtlich im K2PrCl5/Y2HfS5-Typ. Einkristall-Strukturverfeinerungen wurden für K2UI5 und Rb2UCl5 unternommen. Magnetische Suszeptibilitätsmessungen erfolgten mit einem SQUID-Magnetometer von Raumtemperatur bis zur Temperatur des flüssigen Heliums: Eindimensionale (innerhalb einer Kette) und dreidimensionale antiferromagnetische Ordnung wird bei tiefen Temperaturen, abhängig vom Abstand U3+—U3+, beobachtet. Absorptionsspektren wurden zwischen 4000 und 28000 cm-1 aufgenommen. Sie zeigen die für U3+ charakteristischen Übergänge und, abhängig vom Halogenid, sehr starke f - d Übergänge oberhalb 14000 bzw. 15000 cm-1.
    Notes: The ternary uranium(III) halides A2UX5 (A = K, Rb; X = Cl, Br, I) have been prepared from the binary components AX and UX3 in sealed tantalum containers. According to their Guinier X-ray powder patterns, they all crystallize with the K2PrCl5/Y2HfS5 type of structure. Lattice constants for ambient temperature are reported. Single-crystal structure refinemens were undertaken for K2UI5 and Rb2UCl5. Magnetic susceptibility data were recorded with a SQUID magnetometer from liquid helium to room temperature. One-dimensional (intrachain) and three-dimensional antiferromagnetic ordering occur at low temperatures dependent upon the U3+—U3+ distance. Absorption spectra were recorded between 4 000 and 28 000 cm-1. They show f - f transitions typical for U3+ and, depending on the halide, very strong f - d transitions above 14 000 to 15 000 cm-1, respectively.
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