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  • 1H, 31P, 7Li-NMR spectra  (1)
  • Aluminium fluoridehydroxide hydrate  (1)
  • Hexathiodiphosphate(IV)  (1)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 611 (1992), S. 107-113 
    ISSN: 0044-2313
    Keywords: Aluminium fluoridehydroxide hydrate ; thermal behaviour ; decomposition reactions ; gas complexes, HAlF4, H2AlF5 ; thermal analysis, evolved gas analysis, mass spectroscopy ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Thermal Behaviour of Aluminium Fluoridehydroxide Hydrate AlF2.3(OH)0.7(H2O)The thermal decomposition of AlF2,3(OH)0,7(H2O) depends strongly on the partial pressure of the gaseous reaction products and proceeds in three overlapping steps, namely dehydratation, formation of x-ray amorphous Al2O3 and metastable β-AlF3, and formation of α-AlF3 and α-Al2O3. Beside that an exchange of F/OH takes place. The vaporization is mainly determined by the crucible type and pressure conditions, as shown by simultaneous TG-MS measurements too. Main gaseous species are H2O and HF. The gas complexes HAlF4, and H2AlF5 are observed.
    Notes: Der thermische Abbau von AlF2,3(OH)0,7(H2O) wird wesentlich durch den Partialdruck der gasförmigen Reaktionsprodukte bestimmt und erfolgt in drei sich überlagernden Reaktionsstufen, nämlich Entwässerung, Bildung von röntgenamorphen Al2O3 und metastabilen β-AlF3 sowie Bildung von α-AlF3 und α-Al2O3. Daneben erfolgt ein F/OH-Austausch. Das Verdampfungsverhalten wird durch Art der Tiegel sowie Druckbedingungen deutlich beeinflußt, was auch durch simultane TG-MS-Untersuchungen gezeigt wird. Hauptkomponenten der Gasphase sind H2O und HF. HAlF4 und H2AlF5 werden als Gaskomplexe beobachtet.
    Additional Material: 4 Ill.
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  • 2
    ISSN: 0044-2313
    Keywords: K2Fe[P2S6] ; Hexathiodiphosphate(IV) ; Hexathiohypodiphosphate ; Crystal Structure ; Magnetism ; Vibrational Spectrum ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese, Kristallstruktur, Magnetismus und Schwingungsspektrum von Dikaliumeisen(II)hexathiodiphosphat(IV), K2Fe[P2S6]K2Fe[P2S6] wurde aus den Elementen bei 1173 K in evakuierten, abgeschmolzenen Quarzampullen dargestellt. Die Verbindung bildet transparente, orangefarbene, luft- und feuchtigkeitsbeständige Kristalle. K2Fe[P2S6] kristallisiert monoklin, Raumgruppe P21/n (Nr. 14), mit den Gitterkonstanten (T = 298,5 K): a = 6,0622(4), b = 12,172(1) und c = 7,3787(8) Å, β = 101,113(7)°, Z = 2. Der neuartige Strukturtyp (mP22) wird durch Säulen von alternierend flächenverknüpften S6-Oktaedern und trigonalen Antiprismen (beide verzerrt) charakterisiert, die parallel zur a-Achse verlaufen und durch K+-Kationen (KZ 10; {2,6,2}-Polyeder; d(K—S) = 3,231 - 3,845 Å) miteinander verbunden sind. Die S6-Polyeder der Säulen werden alternierend durch Fe (d̄(Fe—S) = 2,577 Å) bzw. P2-Paare zentriert, die zur a-Achse um 73,4° geneigt sind. Die Bindungslängen in den Hexathiodiphosphat(IV)-Anionen [P2S6]4- mit angenäherter 32/m - D3d-Symmetrie betragen d(P—P) = 2,20 und d̄(P—S) = 2,02 Å. Die Titelverbindung ist oberhalb TN = 28 K paramagnetisch mit μ = 4,69 B.M. und ordnet unterhalb TN antiferromagnetisch. Die beobachteten inneren Moden der Raman- und Infrarotspektren von K2Fe[P2S6] stehen im Einklang mit der Faktorgruppenanalyse. Die Schwingungsbanden werden auf der Basis von [P2S6]4--Einheiten unter Berücksichtigung der Abweichungen von der D3d-Symmetrie zugeordnet.
    Notes: K2Fe[P2S6] was synthesized from the elements at 1173 K in sealed quartz tubes. The compound forms transparent orange crystals, stable against air and moisture. K2Fe[P2S6] crystallizes in the monoclinic system, space group P21/n (No. 14), with cell dimensions (T = 298.5 K) a = 6.0622(4), b = 12.172(1) and c = 7.3787(8) Å, β = 101.113(7)°, Z = 2. The novel structure type (mP22) is characterized by columns of alternating face-sharing S6 octahedra and trigonal antiprisms (both distorted) parallel to the a axis, which are interconnected by inserted K+ (CN 10; {2,6,2}-polyhedra; d(K—S) = 3.231 - 3.845 Å). The S6 polyhedra of the columns are centered alternately by Fe (d̄(Fe—S) = 2.577 Å) and P2 pairs which are inclined to the a axis by 73.4°. The bond lengths in the hexathiodiphosphate(IV) anions, [P2S6]4-, with approximate 3 2/m - D3d symmetry, are d̄(P—P) = 2.20 and d̄(P—S) = 2.02 Å. The compound is paramagnetic above TN = 28 K with μ = 4.69 B.M. and orders antiferromagnetically below TN. The internal modes of the observed Raman and FIR spectra of K2Fe[P2S6] are in accord with the factor group analysis, and the spectra are assigned on the basis of [P2S6]4- units, taking into account the deviation from D3d symmetry.
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  • 3
    ISSN: 0044-2313
    Keywords: Li(THF)2[η2-(tBu2P)2P] ; Li(TMEDA)[η2-(tBu2P)2P] ; Li(THF)2[η2-(iPr2P)2P] ; Li(THF)2[η2-(Et2N)2P—P—PtBu2] ; Li(THF)2[η2-(tBu2P—P—PiPr2)] ; (tBu2P)2P—SiMe3 ; crystal structures ; 1H, 31P, 7Li-NMR spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Formation and Structure of Li(THF)2[η2-(tBu2P)2P], Li(TMEDA)[η2-(tBu2P)2P], Li(THF)2[η2-(iPr2P)2P], Li(THF)2[η2-(Et2N)2P—P—PtBu2], Li(THF)2[η2-(tBu2P—P—PiPr2] and (tBu2P)2P—SiMe3The formation and crystal structures of the compounds (tBu2P)2P—SiMe3 1, Li(THF)2[η2-(tBu2P)2P] 2, Li(TMEDA)[η2-(tBu2P)2P] 3, Li(THF)2[η2-(iPr2P)2P] 4, Li(THF)2[η2-(Et2N)2P—P—PtBu2] 5 and Li(THF)2[η2-(tBu2P—P—PiPr2)] 6 are reported. Compounds 3-6 are formed by reacting the corresponding silylated triphosphanes with nBuLi: 2 and 3 result from (tBu2P)2P—SiMe3 1, 4 from (iPrP)2P—SiMe3, 5 from (Et2N)2P—P(SiMe3)—PtBu2 and 6 from tBu2P—P(SiMe3)—PiPr2. 1 crystallizes in the orthorhombic space group P212121 (no. 19) with a = 910.87(7) pm, b = 1132.5(1) pm, c = 2373.5(2) pm (determined at 90 K). The structure determination of 2 was performed at 293 K and 200 K, respectively. 2 crystallizes in the monoclinic space group P21/n (no. 14) with a = 1069.7(3) pm, b = 1802.5(3) pm, c = 1604.0(7) pm, β = 98.11(2)° (200 K); 3 also in P21/n (no. 14) with a = 904.3(2) pm, b = 1936.4(5) pm, c = 1653.2(3) pm, β = 94.52(1)° (200 K). 4 crystallizes monoclinically in C2/c (no. 15) with a = 1650.0(5) pm, b = 945.6(3) pm, c = 1779.8(5) pm, β = 108.81(2)° (200 K); 5 in P21/n (no. 14) with a = 939.4(5) pm, b = 1736.8(6) pm, c = 1943.3(7) pm, β = 98.17(4)° (200 K). All compounds contain Z = 4 molecules in the unit cell.The 1H, 31P and 7Li NMR spectra of 2-6 are discussed.
    Notes: Es wird über die Verbindungen (tBu2P)2P—SiMe3 1, Li(THF)2[η2-(tBu2P)2P] 2, Li(TMEDA) · [η2-(tBu2P)2P] 3, Li(THF)2[η2-(iPr2P)2P] 4, Li(THF)2[η2-(Et2N)2P—P—PtBu2] 5 und Li(THF)2[η2-(tBu2P—P—PiPr2)] 6 berichtet. Letztere bilden sich durch Umsetzung der entsprechenden silylierten Triphosphane mit nBuLi: 2 und 3 aus (tBu2P)2P—SiMe3 1, 4 aus (iPr2P)2P—SiMe3, 5 aus (Et2N)2—P · (SiMe3)—PtBu2, 6 aus tBu2P—P(SiMe3)—PiPr2.1 kristallisiert orthorhombisch in P212121 (Nr. 19) mit a = 910,87(7) pm, b = 1132,5(1) pm, c = 2373,5(2) pm (bei 90 K bestimmt). Die Strukturbestimmung von 2 erfolgte bei 293 K und 200 K. 2 kristallisiert monoklin in P21/n (Nr. 14) mit a = 1069,7(3) pm, b = 1802,5(3) pm, c = 1604,0(7) pm, β = 98,11(2)° (200 K), 3 ebenfalls in P21/n (Nr. 14) mit a = 904,3(2) pm, b = 1936,4(5) pm, c = 1653,2(3) pm, β = 94,52(1)° (200 K). 4 kristallisiert monoklin in C2/c (Nr. 15) mit a = 1650,0(5) pm, b = 945,6(3) pm, c = 1779,8(5) pm, β = 108,81(2)° (200K), 5 in P21/n (Nr. 14) mit a = 939,4(5) pm, b = 1736,8(6) pm, c = 1943,3(7) pm, β = 98,17(4)° (200 K). Alle fünf Verbindungen enthalten jeweils vier Formeleinheiten in der Elementarzelle.Es wird über die Untersuchung der 1H-, 31P- und 7Li-NMR-Spektren der Verbindungen 2-6 berichtet.
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