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  • 1
    ISSN: 1520-510X
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Chester : International Union of Crystallography (IUCr)
    Journal of synchrotron radiation 8 (2001), S. 707-709 
    ISSN: 1600-5775
    Source: Crystallography Journals Online : IUCR Backfile Archive 1948-2001
    Topics: Geosciences , Physics
    Notes: In situ X-ray absorption near edge structure (XANES) investigations were carried out at chlorine K edge and palladium L3 edge to study the mechanism of the thermal decomposition of ammonium hexachloropalladate. The spectra show a characteristic feature for the initial step that might be explained as the formation of the precursor via ligand exchange (Cl ⇒ NH3). Multiple scattering calculations (Feff 8) for the Cl K, Pd and Rh L3 edges were successful in simulating the XANES spectra of the precursor as well as the reference compounds (NH4)2[PdCl4] and (NH4)3[RhCl6].
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  • 3
    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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  • 4
    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.
    Additional Material: 4 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 893-898 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New Azoolefines and their Acidic cleavage to Aryldiimines3-Amino-1-aryl-3′,3′-dimethyl-pyrazolin-4-spiro-2′-oxiran-5-ones (3a-c) undergo ring opening with methoxide forming methyl 3-amino-3-arylazo-propenoates (5a-c). 5a-c are cleaved under acidic conditions. The main products of the cleavage of 5c with methanolic hydrochloric acid are nitrogen, 2, 4, 6-trichloro-benzen (6), 2, 4, 6-trichloro-aniline (9) and 2, 4, 6-trichlorophenylhydrazine (10). Intermediates of the cleavage of 5 are aryldiimines trapped with benzaldehyde as the corresponding benzhydrazides (12a, b).
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  • 6
    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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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 618 (1992), S. 26-29 
    ISSN: 0044-2313
    Keywords: Rhenium complexes ; synthesis ; crystal structure ; thermal behaviour ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis, Structure and Thermolysis of NH4[Re3Br10]NH4[Re3Br10] crystallizes as dark brown single crystals upon slow cooling of a hot, saturated hydrobromic-acid solution of [Re3Br9(H2O)2] after the addition of NH4Br. The crystal structure (monoclinic, C2/m (Nr. 12); Z = 4; a = 1461.6(7), b = 1 085.6(4), c = 1030.3(7) pm, β = 92.63(4)°, Vm = 245.9(4)cm3/mol; R = 0.097, Rw = 0.043) contains [Re3Br12]- units that share two common edges. These chains run along [010] and are held together by NH4+ ions. Each NH4+ is surrounded by eight Br- from four different chains. The first step of the thermal decomposition at 290°C is the disproportionation to ReBr3 (ReCl3 type), rhenium metal and (NH4)2[ReBr6]. Secondly, the internal reduction of (NH4)2[ReBr6] at 390°C to rhenium metal takes place.
    Notes: Aus heißer, gesättigter, bromwasserstoffsaurer Lösung von [Re3Br9(H2O)2] erhält man nach Zugabe von NH4Br beim langsamen Abkühlen dunkelbraune Einkristalle von NH4[Re3Br10]. In der Kristallstruktur (monoklin, C2/m (Nr. 12); Z = 4; a = 1 461,6(7); b = 1 085,6(4); c = 1030,3(7) pm, β = 92,63(4)°, Vm = 245,9(4) cm3/mol; R = 0,097, Rw = 0,043) erstrecken sich entlang [010] doppelt kantenverknüpfte [Re3Br12]--Baueinheiten. Diese Stränge werden durch NH4+-Ionen zusammengehalten, wobei jedes NH4+ von acht Br- aus vier unterschiedlichen Strängen umgeben ist. Der thermische Abbau erfolgt im wesentlichen in zwei Schritten: Bei 290°C entsteht durch Disproportionierung ReBr3 im ReCl3-Typ bzw. Rhenium-Metall neben (NH4)2[ReBr6], das bei 390°C durch “innere Reduktion” zu Rhenium-Metall abgebaut wird.
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  • 8
    ISSN: 0044-2313
    Keywords: Thermolysis ; platinum ; palladium ; rhodium ; ruthenium ; chloro complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Mechanism of the Thermal Decomposition of Ammonium and Ammin Chloro Complexes of Ruthenium, Rhodium, Palladium and PlatinumThe thermolysis of noble metal compounds was investigated by a combination of independent physical (DTA/TG, high-temperature Guinier-Simon-technique) and preparative methods, characterization of the educts, intermediats and products by Guinier X-ray patterns and IR spectroscopy: (a)(NH4)2[PtCl6], (NH4)2[PtCl4], [Pt(NH3)4][PtCl4], [Pt(NH3)4]Cl2, and trans-[Pt(NH3)2Cl2];(b)(NH4)2[PdCl4], [Pd(NH3)4]Cl2, trans-[Pd(NH3)2Cl2], and [Pd(NH3)4][PdCl4];(c)(NH4)2[RhCl5(H2O)], (NH4)3[Rh2Cl9], K2[RhCl5(H2O)], and K2[RhCl5(NH3)];(d)(NH4)2[RuCl5(NH3)] and (NH4)4[Ru2Cl10O] .The most important step of the mechanism of the thermal decomposition is the „internal“ redox reaction between the noble metal cation and the nitrogen atom of the ammine ligand.
    Notes: Durch Kombination von DTA/TG, Hochtemperatur-Guinier-Simon-Aufnahmen und präparativen Methoden, sowie durch Charakterisierung der Edukte, Intermediate und Produkte mittels Röntgenaufnahmen nach dem Guinier-Verfahren und anhand von IR-Spektren, wurde der „thermische Abbau“ von Edelmetallverbindungen eingehend untersucht: (a)(NH4)2[PtCl6], (NH4)2[PtCl4], [Pt(NH3)4][PtCl4], [Pt(NH3)4]Cl2 und trans-[Pt(NH3)2Cl2];(b)(NH4)2[PdCl4], [Pd(NH3)4]Cl2, trans-[Pd(NH3)2Cl2] und [Pd(NH3)4][PdCl4];(c)(NH4)2[RhCl5(H2O)], (NH4)3[Rh2Cl9], K2[RhCl5(H2O)] und K2[RhCl5(NH3)];(d)(NH4)2[RuCl5(NH3)] und (NH4)4[Ru2Cl10O].Der entscheidende Schritt des Mechanismus des „thermischen Abbaus“ ist die „innere“ Reduktion des Edelmetallkations durch den Amminstickstoff.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 1685-1692 
    ISSN: 0044-2313
    Keywords: New oxides of divalent copper ; crystal structure ; MAPLE ; absorption spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis, Crystal Structures, and Absorption Spectra of the New “Cupriosilicates”: K6[CuSi2O8] and Rb4[CuSi2O7]K6[CuSi2O8] and Rb4[CuSi2O7] were obtained by annealing intimate mixtures of K2O and Rb2O, respectively, CuO and SiO2 in sealed Ag cylinders at 500°C as transparent greenish-blue single crystals. The structure solution (IPDS-data Mo Kα; K6[CuSi2O8]: 1292 F2(hkl), R1 = 0.059; wR2 = 0.103 and Rb4[CuSi2O7]: 763 F2(hkl), R1 = 0.049; wR2 = 0.114) confirms the space group P1 for both compounds. K6[CuSi2O8]: a = 619.4(2); b = 665.5(2); c = 753.0(2) pm; α = 83.66(3); β = 87.71(3); γ = 70.19(3)°; Z = 1. Rb4[CuSi2O7]: a = 631.9(9); b = 707.5(10); c = 715.2(6) pm; α = 114.2(1); β = 100.7(1); γ = 107.9(1)°; Z = 1. The Madelung Part of the Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these calculated via Mean Effective Ionic Radii, MEFIR, are given. The absorption spectra of K6[CuSi2O8] and Rb4[CuSi2O7] are discussed in terms of the Angular Overlap Model, AOM.
    Notes: K6[CuSi2O8] und Rb4[CuSi2O7] wurden erstmals durch Tempern innig verriebener Gemenge aus K2O bzw. Rb2O, CuO und SiO2 in verschlossenen Ag-Zylindern bei 500°C in Form von transparenten blaugrünen Einkristallen erhalten. Die Strukturaufklärung (IPDS-Datensätze, Mo-Kα; K6[CuSi2O8]: 1292 F2(hkl), R1 = 0,059; wR2 = 0,103 und Rb4[CuSi2O7]: 763 F2(hkl), R1 = 0,049; wR2 = 0,114) belegt die Raumgruppe P1 für beide Verbindungen. K6[CuSi2O8]: a = 619,4(2); b = 665,5(2); c = 753,0(2) pm; α = 83,66(3); β = 87,71(3); γ = 70,19(3)°; Z = 1. Rb4[CuSi2O7]: a = 631,9(9); b = 707,5(10); c = 715,2(6) pm; α = 114,2(1); β = 100,7(1); γ = 107,9(1)°; Z = 1. Der Madelunganteil der Gitterenergie, MAPLE, sowie Effektive Koordinationszahlen, ECoN, aus Mittleren Fiktiven Ionenradien, MEFIR, erhalten, werden angegeben. Die Absorptionsspektren von K6[CuSi2O8] und Rb4[CuSi2O7] werden anhand des Angular-Overlap-Modells, AOM, diskutiert.
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  • 10
    Publication Date: 2007-11-01
    Print ISSN: 0013-936X
    Electronic ISSN: 1520-5851
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering
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