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  • 1
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The VIS-laser irradiation of enol lactones 1a, b and benzoquinone in an argon atmosphere led to the fenestrane-type oxetane 2a and the propellane-type oxetane 2b, with regioselective preference for the acetal structure. Under an oxygen atmosphere both regioisomeric fenestrane-type 1,2,4-trioxanes 4a and 5a were obtained from enol lactone 1a, while no oxygen trapping to the propellane-type trioxanes was observed with 1b. Significant quantities of photooxygenation products were obtained from both enol lactones 1a, b due to singlet oxygen derived from oxygen quenching of benzoquinone triplets. The present study demonstrates that Qinghaosu analoga are accessible via trapping of Paterno-Büchi triplet 1,4-diradicals by molecular oxygen.
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  • 2
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 557-561 
    ISSN: 0044-2313
    Keywords: TlEu[PS4] ; Tetrathiophosphate(V) ; Crystal Structure ; Vibrational Spectrum ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Kristallstruktur und Schwingungsspektrum von Thallium(I)-Europium(II)-tetrathiophosphat(V), TlEu[PS4]TlEu[PS4] wurde aus den Elementen bei 1 150 K in einer evakuierten Quarzampulle dargestellt. Die Verbindung bildet transparente, orangefarbene, luft- und feuchtigkeitsbeständige Nadeln, die orthorhombisch, Pnma (Nr. 62) mit a = 12,157(2), b = 6,581(1), c = 8,802(2) Å, Z = 4 kristallisieren. Charakteristisch sind diskrete [PS4]3--Anionen, die durch Tl+ und Eu2+ verbunden sind. Sie sind verzerrt tetraedrisch mit P—S-Abständen zwischen 2,028 und 2,043 Å und so angeordnet, daß Liganden benachbarter Gruppen trigonale S6-Prismen bilden, entlang [0 0 1] zu Säulen verknüpft, die parallel (1 0 0) über gemeinsame Kanten zu gewellten Schichten kondensiert sind. Dazwischen sind leere, verzerrte Halbwürfel und zur Hälfte mit P-Atomen besetzte Tetraederlücken Durch die alternierende Besetzung mit Tl+ und Eu2+ sind diese Prismen leicht verzerrt. Man kann daher diese Struktur als eine geordnete, teilweise aufgefüllte Überstruktur des InNi2-Typs auffassen (InInNi4□2tet ≙ TlEuS4P□1tet), aber auch als zentrosymmetrische Variante der TlSn[PS4]-Struktur (Raumgruppe Pna21). Das Schwingungsspektrum entspricht der Strukturbestimmung, die beobachteten Raman- und Infrarotbanden lassen sich zwanglos auf der Basis von [PS4]3- -Einheiten mit C2v-Symmetrie zuordnen.
    Notes: TlEu[PS4] was synthesized from the elements in a sealed quartz ampoule at 1 150 K. The compound forms transparent orange needles, stable in air and moisture. It crystallizes in the orthorhombic system, space group Pnma (No. 62), with cell dimensions a = 12.157(2), b = 6.581(1), c = 8.802(2) Å, Z = 4. The crystal structure consists of discrete [PS4]3- anions interconnected by Tl+ and Eu2+. The tetrahedral [PS4]3- groups are slightly distorted with P—S bond lengths in the range 2.028 to 2.043 Å. These tetrahedral anions are arranged in such a way that the sulfur atoms form columns of distorted trigonal S6 prisms along [0 0 1]. The columns are condensed via common edges to puckered layers parallel to (1 0 0). The interlayer region consists of empty distorted half-cubes and tetrahedral holes, half of them filled by P atoms. The trigonal prisms in the columns are centered alternately by Tl+ and Eu2+. In this way, the structure can be regarded as an ordered superstructure of the InNi2 type, where half of the tetrahedral holes are filled by phosphorus atoms: InInNi4□2tet ≙ TlEuS4P□1tet. TlEu[PS4] is a centrosymmetric variant of the TlSn[PS4] structure type (space group Pna21). The vibrational spectrum is in accordance with the X-ray crystal structure, the Raman and infrared vibrations are assigned on the basis of [PS4]3- units with C2v symmetry.
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  • 4
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Formation and Structure of tert-Butyl(tert-butylamino) [tris(tert-butyloxy)silylthio]-boraneThe smooth addition of the SH bond of (tBuO)3SiSH to the BN bond of tBuB≡NtBu gives the title compound, which crystallizes in the triclinic system, space group P1, with an unexpectedly short BN bond, d(BN) = 137 pm, in a Z configuration.
    Notes: Die SH-Bindung von (tBuO)3SiSH addiert sich glatt an die BN-Bindung von tBuB≡NtBu unter Bildung der Titelverbindung. Diese kristallisiert triklin, Raumgruppe P1, mit einer unerwartet kurzen, Z-konfigurierten BN-Bindung, d(BN) = 137 pm.
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  • 5
    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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  • 6
    ISSN: 0044-2313
    Keywords: Alkali metal germanides and stannides ; Zintl cluster anions ; Vibrational spectra ; Thermal decomposition ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binary germanides M12Ge17 and M4Ge9 (M = Na, K, Rb, Cs) and the stannides M12Sn17 and M4Sn9 (M = K, Rb, Cs) were identified by a combination of direct synthesis, thermogravimetric analysis, vibrational spectroscopy, X-ray powder data and single crystal structure analysis. The M12E17 phases contain the cluster anions [E9]4- and [E4]4- in the ratio 1:2, forming a hierarchical structure with the cluster anions at the atomic positions of the hexagonal Laves phase MgZn2. Like the M4E4 phases, the M4Ge9 compounds are hierarchical derivatives of the cubic Cr3Si structure but with [Ge9]4- anions. The thermogravimetric analyses give strong evidence for the existence of at least one more phase with [E9]4- and [E4]4- clusters and of the clathrate phases M6E136 in addition to the well-known M8E44□2 chlathrates.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 563 (1988), S. 48-52 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Silicon-Sulphur Compounds. 53. Structure of 1,3-Dimethyl-1,1,3,3-tetraphenyldisilthiane1,3-Dimethyl-1,1,3,3-tetraphenyldisilthiane was obtained by an insertion reaction of sulphur with Ph2 MeSiH. The compound crystallizes triclinically (P1; a = 1166.7; b = 1231.1; c = 988.6 pm; α = 113.23; β = 90.34; γ = 112.43°; Z = 2). The X-ray structure analysis shows a bent configuration of the molecule with Si—S—Si = 108.7°. The results are discussed together with the structures of hexaphenyldisilthiane and dimethyltetraphenyldisiloxane.
    Notes: 1,3-Dimethyl-1,1,3,3-tetraphenyldisilthian entsteht aus Schwefel und Ph2MeSiH in einer Einschub-Reaktion. Die Verbindung kristallisiert triklin (P1; a = 1166,7; b = 1231,1; c = 988,6 pm; α = 113,23; β = 90,34; γ = 112,43°; Z = 2). Die Kristallstruktur-analyse ergab eine gewinkelte Konfiguration des Moleküls mit Si—S—Si = 180,7°. Die Ergebnisse werden im Zusammenhang mit der Struktur des Hexaphenyldisilthians und Dimethyltetraphenyl disiloxans diskutiert.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 205-211 
    ISSN: 0044-2313
    Keywords: Tetrapnictidometallates(IV) ; Tetrapnictidotantalates(V) ; Na6ZnO4 structure type ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New Tetrapnictidometallates of Silicon, Germanium, Tin, and Tantalum with the Na6ZnO4 StructureThe tetrapnictidometallates(IV) Na3M3EIVX4 (M = Na/Ca, Na/Sr, Na/Eu; E = Si, Ge, Sn and X = P, As) were prepared from NaX, M′X (M′ = Ca, Sr, Eu) and elemental E in tantalum ampoules at temperature of 1270 K. The tetrapnictidotantalates(V) Na3(Na2Eu)TaP4 and Na3(Na2Eu)TaAs4 were formed by a reaction with the walls of the ampoule. All compounds crystallise hexagonal in the Na6ZnO4 structure type hP22 (P63mc; no. 186; Z = 2) with polar orientated tetrahedron anions [SiX4]8-, [GeX4]8-, [SnX4]8- and [TaX4]7-. The average bondlengths are: d̄(Si—P) = 230.4 pm; d̄(Si—As) = 239.9 pm; d̄(Ge—P) = 237.1 pm; (Ge—As) = 247.8 pm; d̄(Sn—P) = 252.3 pm; d̄(Sn—As) = 261.4 pm; d̄(Ta—P) = 238.3 pm; d̄(Ta—As) = 247.4 pm.
    Notes: Die Tetrapnictidometallate(IV) Na3M3EIVX4 (M = Na/Ca, Na/Sr, Na/Eu; E = Si, Ge, Sn und X = P, As) wurden aus NaX, M'X (M′ = Ca, Sr, Eu) und elementarem E (Tantalampullen, 1270 K) synthetisiert. Die Tetrapnictidotantalate(V) Na3(Na2Eu)TaP4 und Na3(Na2Eu)TaAs4 entstanden bei Wandreaktionen mit dem Ampullenmaterial. Alle Verbindungen kristallisieren hexagonal im Na6ZnO4-Strukturtyp hP22 (P63mc, Nr. 186, Z = 2) mit polar ausgerichteten Tetraederanionen [SiX4]8-, [GeX4]8-, [SnX4]8- und [TaX44]7-. Die mittleren Bindungslängen sind: d̄(Si—P) = 230.4 pm, d̄(Si—As) = 239.9 pm, d̄(Ge—P) = 237.1 pm, d̄(Ge—As) = 247.8 pm, d̄(Sn—P) = 252.3 pm, d̄(Sn—As) = 261.4 pm, d̄(Ta—P) = 238.3 pm, d̄(Ta—As) = 247.4 pm.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 536 (1986), S. 137-146 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Hydroxo Compounds. 12. Crystal Structure and Constitution of Sodium Trihydroxozincate Na[Zn(OH)3] 1The crystal structure of the very sensitive sodium trihydroxozincate Na[Zn(OH)3] 1 has been determined at 190 K. Contrary to the observations of trigonal planar [Zn(OH)3]- anions at 298 K, the structure of 1 at lower temperatures is characterized by 1-dimensional chains ∞1[Zn(OH)2(OH)2/2]- with the much more plausible (distorted) tetrahedral coordination of the Zn atoms (P42bc—C4v 6; Nr. 106; a = 1083.9 pm; c = 530.8 pm; Z = 8; Zn—O = 194.3-200.5 pm). The H positions were determined unambigeously from the X-ray data in complete agreement with calculations of potential profiles. There are pronounced hydrogen bond distances present. The Na atoms are coordinated by (5+1) oxygen atoms (Na—O = 234.8-248.8 pm and 282.7 pm). The noncentric coordination of the atoms as well as the strong anisotropic and anharmonic temperature tensors indicate a second order phase transition between 190 K and 298 K.
    Notes: Die Kristallstruktur des gegen Hydrolyse sehr empfindlichen Natriumtrihydroxozinkats Na[Zn(OH)3] 1 wurde bei 190 K bestimmt. Während bei 298 K trigonal-planare [Zn(OH)3]--Anionen beobachtet wurden, ist die Struktur von 1 bei tieferen Temperaturen durch 1-dimensionale Ketten ∞1[Zn(OH)2(OH)2/2]- mit der wesentlich plausibleren (verzerrten) Tetraederkoordination der Zn-Atome charakterisiert (P42bc—C4v 6; Nr. 106; a = 1083,9 pm; c = 530,8 pm; Z = 8; Zn—O = 194,3-200,5 pm). Die H-Positionen wurden in Übereinstimmung mit Berechnungen der Potentialprofile aus den Beugungsdaten bestimmt. Es treten ausgeprägte H-Brückenbindungen auf. Die Na-Atome sind von (5+1) O-Atomen koordiniert (Na—O = 234,8-248,8 pm, sowie 282,7 pm). Die azentrische Koordination aller Atome, sowie die anisotropen bzw. anharmonischen Tensoren lassen vermuten, daß zwischen 190 K und 298 K ein Phasenübergang 2. Ordnung stattfindet.
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  • 10
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Silicon-Sulfur Compounds. XL. Structure of α,ω-substituted Permethylpolysilanes (SiMe2)nR2, with R = (t-BuO)3SiS and n = 2, 3, 6The α,ω-substituted permethylpolysilanes (SiMe2)nR2 with R = (t-BuO)3SiS and n = 2, 3, 6, were obtained by reaction of α,ω-dichloropermethylpolysilanes with (t-BuO)3SiSH and Et3N. The crystal Structures were Determined. The mean value of the Si—Si bond distances in the polysilane chains is d(Si—Si) = 233.8(7) pm within small variations. However, in the hexasilane a tendency to Stretch the central bond (234.9 pm) may be observed. The mean value of the Si—S bond length is 213.5 pm. A special feature of the conformation of the disilane and hexasilane derivatives, is the almost in a plane arranged zigzag chain of six or ten atoms, respectively. However, the chain of seven atoms in trisilane derivative is different due to a 120° torsion around the third bond in this chain. Some Structural Details are discussed.
    Notes: α,ω-substituierte Permethylpolysilane (SiMe2)nR2 mit R = (t-BuO)3SiS und n = 2, 3, 6 wurden durch Reaktion der α,ω-Dichloropermethylsilane mit (t-BuO)3SiSH und Et3N dargestellt. Die Kristallstrukturen wurden bestimmt. In Den Polysilanketten liegen Bindungslängen mit geringen Variationen bei d(Si—Si) = 233,8(7) pm. Lediglich im Hexasilan wird eine Tendenz zur Streckung der zentralen Bindung auf 234,9 pm sichtbar. Der Mittelwert für die Si-S-Bindungslängen beträgt 213,5 pm. Ein besonderes Merkmal der Konformation Von Disilan und Hexasilan ist die nahezu in einer Ebene verlaufende Zick-Zack-Kette aus sechs bzw. zehn Atomen. Im Trisilan ist die Kette aus sieben Atomen dagegen an der dritten Bindung um 120° tordiert. Die Einzelheiten der Strukturen werden im Zusammenhang diskutiert.
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