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  • Inorganic Chemistry  (727)
  • 1995-1999
  • 1990-1994  (727)
  • 1950-1954
  • 1993  (727)
Collection
Keywords
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Years
  • 1995-1999
  • 1990-1994  (727)
  • 1950-1954
Year
  • 101
    Electronic Resource
    Electronic Resource
    Darstellung von N-Methyl-N-chlornitryl-hexafluorometallaten ON(Cl)CH3+MF6- (M = As, Sb) (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1743-1746 
    Details
    ISSN: 0044-2313
    Keywords: N-metyl-N-chloronitryl hexafluoro metallates ; nitryl cation ; vibrational spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation of N-Methyl-N-chlornitryl Hexafluoro Metallates ON(Cl)CH3+MF6- (M = As, Sb).The preparation of ON(Cl)CH3+MF6- (M = As, Sb) by methylation of ONCl with CH3OSO+MF6- (M = As, Sb) is reported. Both salts were unlimited stable at - 78°C. The nitryl cation which is isoelectronic with acetyl chloride was identified by vibrational spectroscopy as N-chloro-N-hydroxy-methaneiminium cation in the solid state.
    Notes: Die Darstellung der N-Methyl-N-chlornitryl-hexafluorometallate ON(Cl)CH3+MF6- (M = As, Sb) erfolgt durch Methylierung von ONCl mit CH3OSO+MF6-. Beide Salze sind unterhalb von - 78°C unbegrenzt haltbar. Das mit Acetylchlorid isoelektronische Nitrylkation erfährt im Festkörper nach schwingungsspektroskopischen Untersuchungen eine Tautomerie zu einem N-Chlor-N-hydroxo-methaniminium-Kation.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19936191020
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  • 102
    Electronic Resource
    Electronic Resource
    Low-spin Manganphthalocyanine: Darstellung, Eigenschaften und elektronisches Raman-Spektrum von Di(cyano)phthalocyaninatomanganat(III) und -(II) (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1729-1737 
    Details
    ISSN: 0044-2313
    Keywords: Di(cyano)phthalocyaninatomanganate(III), Di(cyano)phthalocyaninatomanganate(II) ; uv-vis, nir, mir, fir, resonance Raman spectra ; electronic Raman spectrum ; cyclovoltammetry ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Low Spin Manganese Phthalocyanines: Preparation, Properties and Electronic Raman Spectrum of Di(cyano)phthalocyaninatomanganate(III) and -(II).Iodophthalocyaninatomanganese(III) reacts with cyanide in acetone to yield di(cyano)phthalocyaninatomanganate(II), in dichloromethane, however di(cyano)phthalocyaninatomanganate(III) is formed. Both complexes are isolated as (n-Bu4N)-salts. In the cyclovoltammogram the redox couple MnII/MnIII is attributed to E1/2 = - 0.22 V and the first ringoxidation Pc(2 -)/Pc(1 -) to E1/2 = 0.75 V. The paramagnetic salts have magnetic moments (μeff = 2.11 resp. 2.95 B.M.) typical for the low spin ground state of MnII resp. MnIII (S = 1/2 resp. 1). The uv-vis-nir spectra are discussed. Comparison with the dicyano-complexes of CrIII, FeII/III and CoIII indicates that the multiple “extra bands” between 4 and 23 kK should be assigned to spin allowed trip-multiplets. The vibrational spectra are discussed. νas(Mn—C)(a2u) is found at 350 cm-1, νas(C—N)(a2u; cyanide) at 2 092 (MnII) and 2 114 cm-1 (MnIII). The Raman spectra are dominated by resonance Raman(RR) effects. With variable-wavelength excitation polarized, depolarized and anomalously polarized vibrations assigned to phthalocyanine skeletal modes are selectively RR-enhanced for the MnII complex. Intensive lines between 1 650 and 3 300 cm-1 are due to combinations and overtones of the a2g vibrations at 1 492 and 1 602 cm-1. In the 10 K Raman spectrum of (n-Bu4N)[Mn(CN)2Pc(2 -)] intraconfigurational transitions Γ1 → Γ4 and Γ1 → Γ3, Γ5 resulting from the splitting of the 3T1g ground state of MnIII (Oh symmetry) by spin-orbit coupling are observed as anomalously polarized and depolarized lines at 172 and 287 cm-1.
    Notes: Iodophthalocyaninatomangan(III) reagiert mit Cyanid in Aceton zu Di(cyano)phthalocyaninatomanganat(II), in Dichlormethan dagegen zu Di(cyano)phthalocyaninatomanganat(III). Beide Komplexe werden als (n-Bu4N)-Salze isoliert. Im Cyclovoltammogramm liegt das Halbstufenpotential für das Redoxpaar MnII/MnIII bei - 0,22 V und das der ersten Ringoxydation Pc(2 -)/Pc(1 -) bei 0,75 V. Die paramagnetischen Salze haben die für low-spin Grundzustände von MnII bzw. MnIII (S = 1/2 bzw. 1) typischen magnetischen Momente: μeff = 2,13 bzw. 2,95 B.M. Die UV-VIS-NIR Spektren werden diskutiert. Der Vergleich mit denen der Dicyano-Komplexe von CrIII, FeII/III und CoIII zeigt, daß es sich bei den zahlreichen “Extra-Banden” zwischen 4 und 23 kK um spin-erlaubte Trip-Multipletts handelt. Die Schwingungsspektren werden diskutiert. νas(Mn—C)(a2u) liegt bei 350 cm-1, νas(C—N)(a2u; Cyanid) bei 2 092 (MnII) bzw. 2 114 cm-1 (MnIII). Die Raman-Spektren zeigen ausgeprägte Resonanz-Raman(RR)-Effekte, so daß je nach Anregungsbedingung selektiv für den MnII-Komplex polarisierte, depolarisierte und anomal polarisierte Schwingungen RR-verstärkt werden, die Phthalocyanin-Gerüstschwingungen zugeordnet werden. Die intensiven Linien zwischen 1 650 und 3 300 cm1 beruhen auf Ober- und Kombinationsschwingungen mit den a2g-Schwingungen bei 1 492 und 1 602 cm-1. Im 10 K RR-Spektrum von (n-Bu4N) [Mn(CN)2Pc(2 -)] werden die aus der Aufspaltung des 3T1g-Grundzustandes von MnIII (Oh-Symmetrie) durch Spin-Bahn-Kopplung resultierenden Intrakonfigurationsübergänge Γ1 → Γ4 und Γ1 → Γ3, Γ5 als anomal polarisierte und depolarisierte Linie bei 172 und 287 cm-1 beobachtet.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19936191018
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  • 103
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    Electronic Resource
    Untersuchungen zum chemischen Transport der wasserfreien Europiumchloride EuCl2, Eu5Cl11, Eu4Cl9, Eu14Cl33 und EuCl3 mit AlCl3Zum Gedenken an Professor Harald Schäfer (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1747-1754 
    Details
    ISSN: 0044-2313
    Keywords: Europium chlorides ; chemical transport reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigations on the Chemical Transport of the Anhydrous Europium Chlorides EuCl2, Eu5Cl11, Eu4Cl9, Eu14Cl33 and EuCl3 with AlCl3.Aluminium trichloride is known as a versatile transporting agent for rare-earth trichlorides, but in case of europium the dichloride EuCl2 as well as the mixed-valence compounds Eu5Cl11, Eu4Cl9 and Eu14Cl33 can be chemically transported, too. The observed transport directions are discussed in terms of partial-pressure and solubility diagrams. Under appropriate conditions the gas-phase complex Eu(AlCl4)2 is obtained as a crystalline solid. Being isostructural with Sr(AlCl4)2, the crystal structure of which has been determined very recently, Eu(AlCl4)2 is the first chloroaluminate of a rare-earth element in the divalent state.
    Notes: Aluminium-trichlorid ist als vielseitig einsetzbares Transportmittel für Lanthanoid-trichloride bekannt; im Falle von Europium lassen sich aber auch das Dichlorid sowie die Gemischtvalenzverbindungen Eu5Cl11, Eu4Cl9 und Eu14Cl33 mit AlCl3 chemisch transportieren. Die beobachteten Transportrichtungen werden anhand von berechneten Partialdruck- und Löslichkeitsdiagrammen diskutiert. Unter geeigneten Bedingungen tritt der Gasphasenkomplex Eu(AlCl4)2 als feste Substanz auf. Diese Verbindung ist das erste Chloroaluminat eines Lanthanoid-Elements im zweiwertigen Zustand; sie wird kristallographisch charakterisiert und ihre Isotypie mit Sr(AlCl4)2 sichergestellt.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/zaac.19936191021
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  • 104
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    Electronic Resource
    [Na · Triglyme]2[S(BH3)4]: Ein Salz des neuen Anions Tetrakis(boran)sulfat(2 - ) Kristallstruktur und theoretische Untersuchung der MolekülstrukturProfessor Heinrich Nöth zum 65. Geburtstage gewidmet (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1353-1359 
    Details
    ISSN: 0044-2313
    Keywords: Bis[triglymesodium(1+)][Tetrakis(borane)sulfate(2-)], [Na · Triglyme]2[S(BH3)4] ; preparation ; crystal structure ; SCF calculations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: [Na · Triglyme]2[S(BH3)4]: a Salt of the New Anion Tetrakis(borane)sulfate(2- ). Crystal Structure and Theoretical Investigation of the StructureNa[H3B-m̈2-S(B2H5)] 1 is produced by the reaction between NaSH and THF · BH3, under dehydrogenation. 1 is also formed as the first 11B-NMR-spectroscopically detectable reaction product by the reaction between anhydrous Na2S and THF · BH3. Adducts of BH3 with the S2- ion are not detectable in THF. The anion [S(BH3)4]2- can however be obtained, by the addition of NaBH4 to 1 in diglyme or triglyme respectively: [Na  -  Triglyme]2[S(BH3)4] 2. 2 crystallizes in the monoclinic space group P21/n (Nr. 14). Structural data of 1 and 2 have been calculated by SCF methods. The anion of 2 may be viewed either as an adduct of B2H6 with S2-, or as a bridge substituted thia derivative of B2H7-; furthermore the anion of 2 is isoelectronic and isostructural with the SO42- ion.
    Notes: Bei der Reaktion zwischen NaSH und THF · BH3 entsteht unter H2-Abspaltung Na[H3B-m̈2-S(B2H5)] 1. 1 entsteht auch als erstes 11B-NMR-spektroskopisch nachweisbares Reaktionsprodukt bei der Reaktion zwischen wasserfreiem Na2S und THF · BH3. Addukte von BH3 an das S2--Ion lassen sich in THF als Lösungsmittel nicht nachweisen. Das neue Anion [S(BH3)4]2- kann jedoch durch Addition von NaBH4 an 1 in Diglyme bzw. Triglyme erhalten werden: [Na · L]2[S(BH3)4] 2. 2 kristallisiert monoklin in der Raumgruppe P21/n (Nr. 14). Aus SCF-Rechnungen erhielten wir die Strukturparameter für 1 und 2. Das Anion von 2 kann sowohl als Addukt von B2H6 an S2- als auch als brückensubstituiertes Thia-Derivat des B2H7--Ions aufgefaßt werden; ferner ist es isoelektronisch und isostrukturell mit dem SO42-- Ion.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19936190806
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  • 105
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    Synthesis, structure, and X-ray absorption spectra of LixNbO2 and NaxNbO2 (x ≤ 1) (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1369-1373 
    Details
    ISSN: 0044-2313
    Keywords: Ternary niobium oxides ; synthesis ; crystal structure ; X-ray absorption near-edge structure (XANES) studies ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Darstellung, Struktur und Röntgenabsorptionsspektren von LixNbO2 und NaxNbO2 (x ≤ 1)Zwei Serien von Verbindungen, LixNbO2 und NaxNbO2, wurden durch Oxidation von LiNbO2 und NaNbO2 dargestellt. Die Auswertung von Neutronenbeugungsexperimenten ergibt eine vollbesetzte Lithium-Lage für x = 1. Auch wenn sich die Kristallsymmetrie für x 〈 1 nicht ändert, wie durch Guinier-Aufnahmen gezeigt wird, zeigen die Spektren der Nb—LIII-Kanten doch signifikante Änderungen, die auf eine abnehmende Besetzung der Nb-d-Zustandsdichte hinweisen.
    Notes: The two series of compounds, LixNbO2 and NaxNbO2, were synthesized from LiNbO2 and NaNbO2 with oxidizing agents. From neutron diffraction, it is concluded that the Li position is fully occupied for x = 1. Even though the long-range crystal symmetry does not seem to change for x 〈 1, as monitored by Guinier X-ray powder patterns, the Nb—LIII XANES spectra exhibit significant spectral variations with x which reflect changes in the unoccupied d-density of states.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19936190808
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  • 106
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    Neue Phosphido-verbrückte Mehrkernkomplexe des Ag, Cd und Zn Die Kristallstrukturen von [Ag4(PPh2)4(PMe3)4], [Ag6(PPh2)6(PtBu3)2] und [M4Cl4(PPh2)4(PnPr3)2] (M = Zn, Cd)Professor Heinrich Nöth zum 65. Geburtstage gewidmet (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1360-1368 
    Details
    ISSN: 0044-2313
    Keywords: Multinuclear phosphido-bridged Ag-, Zn- and Cd-Complexes ; synthesis ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New Phosphido-bridged Multinuclear Complexes of Ag, Cd and Zn. The Crystal Structures of [Ag4(PPh2)4(PMe3)4], [Ag6(PPh2)6(PtBu3)2] and [M4Cl4(PPh2)4(PnPr3)2] (M = Zn, Cd)AgCl reacts with Ph2PSiMe3 in the presence of a tertiary Phosphine PMe3 or PtBu3 to form the multinuclear complexes [Ag4(PPh2)4(PMe3)4] (1) and [Ag6(PPh2)6(PtBu3)2] (2). In analogy to that MCl2 reacts with Ph2PSiMe3 in the presence of PnPr3 to form the two multinuclear complexes [M4Cl4(PPh2)4(PnPr3)2] (M = Zn (3), Cd (4)). The structures were characterized by X-ray single crystal structure analysis (1: space group Pna21 (Nr. 33), Z = 4, a = 1 313.8(11) pm, b = 1 511.1(6) pm, c = 4 126.0(18) pm, 2: space group P-1 (Nr. 2), Z = 2, a = 1 559.0(4) pm, b = 1 885.9(7) pm, c = 2 112.4(8) pm, α = 104.93(3)°, β = 94.48(3)°, γ = 104.41(3)°; 3: space group C2/c (Nr. 15), Z = 4, a = 2 228.6(6) pm, b = 1 847.6(6) pm, c = 1 827.3(6) pm, β = 110.86(2); 4: space group C2/c (Nr. 15), Z = 4, a = 1 894.2(9) pm, b = 1 867.9(7) pm, c = 2 264.8(6) pm, β = 111.77(3)°). 3 and 4 may be considered as intermediates on the route towards polymeric [M(PPh2)2]n (M = Zn, Cd).
    Notes: AgCl reagiert mit Ph2PSiMe3 in Gegenwart der tertiären Phosphane PMe3 und PtBu3 unter Bildung der mehrkernigen Komplexe [Ag4(PPh2)4(PMe3)4] (1) und [Ag6(PPh2)6(PtBu3)2] (2). Analog dazu reagiert MCl2 mit Ph2PSiMe3 und PnPr3 zu den mehrkernigen Komplexen [M4Cl4(PPh2)4(PnPr3)2] (M = Zn 3), Cd (4)). Die Struktur der Komplexe konnte durch Kristallstrukturanalysen aufgeklärt werden (1: Raumgruppe Pna21 (Nr. 33), Z = 4, a = 1 313,8(11) pm, b = 1 511,1(6) pm, c = 4 126,0(18) pm, 2: Raumgruppe P1 (Nr. 2), Z = 2, a = 1 559,0(4) pm, b = 1 885,9(7) pm, c = 2 112,4(8) pm, α = 104,93(3)°, β = 94,48(3)°, γ = 104,41(3)°; 3: Raumgruppe C2/c (Nr. 15), Z = 4, a = 2 228,6(6) pm, b = 1 847,6(6) pm, c = 1 827,3(6) pm, β = 110,86(2); 4: Raumgruppe C2/c (Nr. 15), Z = 4, a = 1 894,2(9) pm, b = 1 867,9(7) pm, c = 2 264,8(6) pm, β = 111,77(3) 3 und 4 können als Vorstufen auf dem Weg zur Bildung von polymerem [M(PPh2)2]n (M = Zn, Cd) angesehen werden.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19936190807
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  • 107
    Electronic Resource
    Electronic Resource
    Metallothermische Reduktion des Tribromids und -iodids von Neodym mit Alkalimetallen (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1379-1383 
    Details
    ISSN: 0044-2313
    Keywords: Metallothermic Reductions ; Dibromides ; Diiodides ; Ternary Halides ; Neodymium ; Crystal Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metallothermic Reduction of the Tribromide and -iodide of Neodymium with Alkali MetalsMetallothermic reduction (700-800°C, 2-3d, tantalum capsules) of NdX3 (X = Br, I) with an equimolar amount of alkali metal (A = Li—Rb) results in the case of lithium and sodium (except for the system Li/NdBr3) in the formation of the dihalides NdX2 (NdBr2 with the PbCl2-type, NdI2 with the SrBr2-type of structure). With A = K and Rb, KNd2Br5, RbNd2Br5, RbNd2I5 and “K8Nd7I25” are obtained. The first three crystallize with the monoclinic TlPb2Cl5-type (space group P21/c), the latter with the orthorhombic K2PrCl5-type of structure (space group Pnma) containing both Nd3+ and Nd2+.
    Notes: Die metallothermische Reduktion (700-800°C, 2-3d, Tantalampulle) von NdX3 (X = Br, I) mit äquimolaren Mengen an Alkalimetall (A = Li—Rb) führt im Falle von Lithium und Natrium (mit Ausnahme von NdBr3/Li) zu den Dihalogeniden NdX2 (NdBr2 im PbCl2-Typ, NdI2 im SrBr2-Typ). Bei der Umsetzung mit Kalium und Rubidium erhält man KNd2Br5, RbNd2Br5 bzw. RbNd2I5, die im monoklinen TlPb2Cl5-Typ (Raumgruppe P21/c) kristallisieren, sowie das isostrukturelle “K8Nd7I25”, das neben Nd2+ auch Nd3+ enthält und zum K2PrCl5-Typ gehört (orthorhombisch, Raumgruppe Pnma).
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/zaac.19936190810
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  • 108
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    Metallothermische Reduktion des Tribromids und -iodids von Dysprosium mit Alkalimetallen (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1374-1378 
    Details
    ISSN: 0044-2313
    Keywords: Metallothermic Reduction ; Dibromides ; Diiodides ; Ternary Halides ; Dysprosium ; Crystal Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metallothermic Reduction of the Tribromide and -iodide of Dysprosium with Alkali MetalsMetallothermic reduction (900-1000°C, 2-3 d, tantalum capsules) of DyX3 (X = Br, I) with alkali metals (A = Li—Cs) results in the case of lithium and sodium (except for the system DyBr3/Li) in the formation of the dihalides DyX2 (DyI2 with the CdCl2-type, DyBr2 with the SrI2-type of structure). The reduction of DyI3 with potassium leads to K1.71DyI4 which crystallizes hexagonally with a = 1 446.7(2) pm and c = 473.3(1) pm, space group P62m (Z = 3). In K1.71DyI4, [DyI6]-octahedra are edge-connected forming chains along [001] that are linked via K+. With A = K, Rb, Cs, variants of the perovskite-type of structure with the composition ADyX3 are obtained. They crystallize with the tetragonal NaNbO3-II-type (CsDyBr3) or with the orthorhombic GdFeO3-type of structure (KDyBr3, RbDyX3, CsDyI3).
    Notes: Bei der metallothermischen Reduktion (Tantalampulle, 900-1 000°C, 2-3 d) von DyX3 (X = Br, I) mit den Alkalimetallen (A = Li—Cs) erhält wird im Falle von Lithium und Natrium (außer im System DyBr3/Li) die Dihalogenide DyX2 (DyI2 im CdCl2-Typ, γyBr2 im SrI2-Typ). Die Reduktion von DyI3 mit Kalium führt zu K1,71DyI4, das hexagonal mit a = 1 446,7(2) pm, c = 473,3(1) pm, Z = 3 in der Raumgruppe P62m kristallisiert: [DyI6]-Oktaeder werden über Kanten längs [001] zu Ketten verknüpft, die durch K+-Ionen verbunden werden. Die Reduktion von DyBr3 mit Kalium, Rubidium und Caesium bzw. DyI3 mit Rubidium und Caesium führen zu Perowskitvarianten ADyX3, die bis auf CsDyBr3 (tetragonaler NaNbO3-II-Typ), im orthorhombischen GdFeO3-Typ kristallisieren.
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    URL: http://dx.doi.org/10.1002/zaac.19936190809
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  • 109
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    [M9C4O]I8 (M = Y, Ho, Er, Lu), reduzierte Selten-Erd-Iodide mit gewellten Metall-Doppelschichten und zwei verschiedenen interstitiellen AtomenProfessor Hans Joachim Berthold zum 70. Geburtstage gewidmet (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1384-1388 
    Details
    ISSN: 0044-2313
    Keywords: Rare-Earth Iodides ; Synthesis ; Crystal Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: [M9C4O]I8 (M = Y, Ho, Er, Lu), Reduced Rare-Earth Iodides with Waved Metal Double Layers and Two Different Interstitial Atoms[M9C4O]I8 (M = Y, Ho, Er, Lu) are examples of reduced rare-earth iodides with two different interstitial atoms. The compounds were synthesized from appropriate mixtures of MI3, M, C and M2O3 at 1 050°C in arc-welded tantalum containers. The X-ray structure analysis of a single crystal of [Y9C4O]I8 (orthorhombic, Pmmn (Nr. 59), Z = 2, a = 2 912.7(6) pm, b = 384.17(4) pm, c = 1 080.29(9) pm, R = 0.084, Rw = 0.053) exhibits octahedrally coordinated carbon in “plane” sections besides tetrahedrally coordinated oxygen in the “bend” of waved metal double layers. These double layers are stacked alternately with waved iodine double layers along [001].
    Notes: Mit [M9C4O]I8 (M = Y, Ho, Er, Lu) wurden reduzierte Selten-Erd-Iodide erhalten, die zwei verschiedene interstitielle Atomsorten enthalten. Die Synthese erfolgt aus geeigneten Gemengen von MI3, M, C und M2O3 bei 1 050°C in verschweißten Tantalampullen. Die Röntgenstrukturanalyse an einem Einkristall von [Y9C4O]I8 (orthorhombisch, Pmmn (Nr. 59), Z = 2, a = 2 912,7(6) pm, b = 384,17(4) pm, c = 1 080,29(9) pm, R = 0,084, Rw = 0,053) zeigt, daß neben oktaedrisch umgebenen Kohlenstoffatomen in “planaren” Abschnitten, tetraedrisch koordinierte Sauerstoffatome in “Knickstellen” gewellter Metall-Doppelschichten vorliegen. Diese Doppelschichten sind alternierend mit gewellten Iod-Doppelschichten längs [001] gestapelt.
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    URL: http://dx.doi.org/10.1002/zaac.19936190811
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  • 110
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    Zur elektronischen Struktur von [Y9C4O]I8Professor Hans Joachim Berthold zum 70. Geburtstage gewidmet (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1389-1392 
    Details
    ISSN: 0044-2313
    Keywords: [Y9C4O]I8 ; electronic structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Electronic Structure of [Y9C4O]I8The new [Y9C4O]I8 structure exhibits striking similarities with layered structures of the well-known rare-earth metal carbide halides [M2C]X2 and [M2C2]X2 (M = rare-earth metal, X = halide) which already have been studied concerning their electronic structures and conductivities. In contrast to the last compounds, [Y9C4O]I8 formally contains one extra electron. This electron appears to be delocalized in various metallic orbitals. The oxygen atoms which are located in the bent sections in the metal double layers as well as the halide double layers in the structure are considered to act as barriers for electronic mobility. Therefore a one-dimensional metallic conductivity is expected to be dominant.
    Notes: Die neue Struktur von [Y9C4O]I8 zeigt eine auffallende Verwandtschaft zu den seit längerer Zeit bekannten Schichtstrukturen der Selten-Erd-Metall-Carbidhalogenide [M2C]X2 sowie [M2C2]X2 (M = Selten-Erd-Metall, X = Halogen), deren elektronische Strukturen und Leitfähigkeitseigenschaften bereits intensiv untersucht wurden. Im Gegensatz zu diesen Verbindungen besitzt [Y9C4O]I8 formal ein zusätzliches Elektron. Dieses Elektron ist über unterschiedliche Metallorbitale delokalisiert. Dabei stellen die Sauerstoffatome in den “Knickstellen” der Metallschichten sowie die Halogendoppelschichten in der Struktur Barrieren für die Elektronenbeweglichkeit dar, weshalb für die Titelverbindung eine eindimensionale metallische Leitfähigkeit dominieren sollte.
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    Synthese und Bau von (4-Picolinium)2[LnCl4(H2O)3]Cl (Ln = Eu, Ho)Professor Hans Joachim Berthold zum 70. Geburtstage gewidmet (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1393-1396 
    Details
    ISSN: 0044-2313
    Keywords: Preparation ; crystal structure ; complex chlorides of lanthanides ; pentagonal bipyramid ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Structure of (4-Picolinium)2[LnCl4(H2O)3]Cl (Ln = Eu, Ho)The complex water containing chlorides (4-Picolinium)2[LnCl4(H2O)3]Cl (Ln = Eu, Ho) were prepared for the first time. The crystal structures were determined on single crystals by X-ray methods. The isotypic compounds crystallize with triclinic symmetry, space group P-1, Z = 2. Surprisingly the structures contain the complex anions [LnCl4(H2O)3]- (Ln = Eu, Ho) where the ligands form a distorted pentagonal bipyramid, which to our knowledge has not been observed in lanthanide compounds till now.
    Notes: Die komplexen wasserhaltigen Chloride (4-Picolinium)2[LnCl4(H2O)3]Cl (Ln = Eu, Ho) wurden erstmals dargestellt und die Kristallstrukturen anhand von röntgenographischen Einkristalluntersuchungen bestimmt. Die isotypen Verbindungen kristallisieren in der triklinen Raumgruppe P1, Z = 2. Überraschend sind die Liganden in den komplexen Anionen [LnCl4(H2O)3]- (Ln = Eu, Ho) in Form einer verzerrten pentagonalen Bipyramide angeordnet, die unseres Wissens bislang bei keiner Lanthanidverbindung beobachtet wurde.
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    [K(15-Krone-5)2]2Te8  -  ein bicyclisches Polytellurid (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1414-1418 
    Details
    ISSN: 0044-2313
    Keywords: Octatelluride, Synthesis, Crystal Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: [K(15-Crown-5)2]2Te8 - a Bicyclic PolytellurideThe octatelluride [K(15-crown-5)2]2Te8 has been synthesized by the oxydation of a potassium tritelluride solution in dimethylformamide by iron(III) chloride in the presence of 15-crown-5, forming black crystals, which were characterized by an X-ray structure determination. Space group Pca21, Z = 4, 4 548 observed unique reflections, R = 0.048. Lattice dimensions at -70°C: a = 1 881(1), b = 2 211(2), c = 1 530(1) pm. The structure consists of cations [K(15-crown-5)2]+, in which the potassium ions are sandwichlike coordinated by the oxygen atoms of the two disordered crown ether molecules, and of bicyclic Te82- ions. In these anions a Te2+ ion is chelated in a planar fashion by a Te32- and a Te42- unit.
    Notes: Das Octatellurid [K(15-Krone-5)2]2 Te8 entsteht durch Oxydation einer Kaliumtritelluridlösung in Dimethylformamid durch Eisen(III)-chlorid in Gegenwart von 15-Krone-5 als schwarze Kristalle, die wir durch eine röntgenographische Strukturanalyse charakterisiert haben. Raumgruppe Pca21, Z = 4, 4 548 beobachtete unabhängige Reflexe, R = 0,048. Gitterabmessungen bei -70°C: a = 1 881(1), b = 2 211(2), c = 1 530(1) pm. Die Struktur besteht aus Kationen [K(15-Krone-5)2]+, in denen die Kaliumionen sandwichartig von den O-Atomen der fehlgeordneten Kronenethermoleküle umgeben sind, und aus bicyclischen Te82--Ionen. In ihnen ist ein Te2+-Ion planar von je zwei Te-Atomen eines Te32-- und eines Te42--Ions chelatartig umgeben.
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    Synthese und Kristallstruktur des Nitrido-Oxalato-Osmats PPh4{Na(15-Krone-5)[OsNCl3(C2O4)]} (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1409-1413 
    Details
    ISSN: 0044-2313
    Keywords: Nitrido Oxalato Complex of Osmium ; Synthesis ; NMR Spectra ; Crystal Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Crystal Structure of the Nitrido Oxalato Osmate PPh4{Na(15-Crown-5)[OsNCl3(C2O4)]}The title compound has been prepared by slow reaction of PPh4[OsNCl4] with sodium oxalate in boiling dichloromethane in the presence of 15-crown-5, forming violet crystals, which were characterized by an X-ray structure determination. Space group P21/c, Z = 4, 4 769 observed unique reflections, R = 0.035. Lattice dimensions at -80°C: a = 1 931.4, b = 1 178.7, c = 1 764.1 pm, β = 99.39°. The structure consists of PPh4+ ions and ion pairs {Na(15-crown-5)[OsNCl3(C2O4)]}-, in which the osmium atom is distortedly octahedrally coordinated by the nitrido ligand, by three chlorine atoms, and by two oxygen atoms of the oxalato group. The remaining oxygen atoms of the oxalato ligand are coordinated to the sodium atom, which, together with the five oxygen atoms of the crown ether molecule, gets coordination number seven.
    Notes: Die Titelverbindung entsteht in langsamer Reaktion aus PPh4[OsNCl4] und Natriumoxalat in Gegenwart von 15-Krone-5 in siedendem Dichlormethan. Die tiefvioletten Kristalle wurden durch eine röntgenographische Strukturanalyse charakterisiert. Raumgruppe P21/c, Z = 4, Strukturlösung mit 4 769 beobachteten unabhängigen Reflexen, R = 0,035. Gitterkonstanten bei -80°C: a = 1 931,4; b = 1 178,7; c = 1 764,1 pm; β = 99,39°. Die Struktur besteht aus PPh4+-Ionen und Ionenpaaren {Na(15-Krone-5)[OsNCl3(C2O4)]}-, in denen das Osmiumatom verzerrt oktaedrisch von einem terminalen Nitridoliganden, von drei Chloratomen und von zwei Sauerstoffatomen der Oxalatogruppe koordiniert ist. Die beiden übrigen O-Atome der Oxalatogruppe sind mit dem Natriumion koordiniert, so daß dieses zusammen mit den Sauerstoffatomen des Kronenethers die Koordinationszahl sieben erreicht.
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    Über die Kristallstruktur von In3Mo11O17 sowie über physikalische Eigenschaften oligomerer Oxomolybdate (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1397-1408 
    Details
    ISSN: 0044-2313
    Keywords: Oxomolybdates ; Cluster ; X-Ray Crystal Structure ; Electrical Resistivity ; Magnetic Susceptibility ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Crystal Structure of In3Mo11O17 and the Physical Properties of Oligomeric OxomolybdatesIn3Mo11O17 is characterized by its molybdate framework Mo22O348- belonging to the general series Mo4n+2O6n+4x- (with n = 5). The phase grows in star-like aggregates and crystallizes within the orthorhombic system (a = 988.0(2) pm, b = 951.2(2) pm, c = 3 176.7(4) pm). There are oligomeric clusters built from five trans edge-sharing Mo6 octahedra, surrounded by O atoms over all empty edges according to the Aufbau principle Mo22O18iO4/2i-iO28/2i-a. In the remaining structural channel one finds an In68+ polycation which is geometrically equivalent with the one of In11Mo40O62. The Mo - O and Mo - Mo distances within the cluster are the same like in In11Mo40O62, too, but there are shorter inter cluster distances (306 pm) in In3Mo11O17. Disorder in the structure may be understood in terms of the presence of constitutional isomers.While the electrical resistivity of PbMo5O8 resembles the one of a strongly disturbed metal (with a local minimum around 120 K), the temperature characteristic of Tl0.8Sn0.6Mo7O11 is typical for a semiconductor. Oxomolybdates with even longer oligomers like In11Mo40O62 and In3Mo11O17 show metallic conductivity. This course corresponds with the sizes of the clusters and their electronic intercoupling which can be estimated from the specific lengths of the inter cluster distances.The effective magnetic moment grows with increasing cluster length from 0.97 μB (PbMo5O8) to 1.40 μB (In11Mo40O62) per cluster (exception: In3Mo11O12), and so does the contribution of the temperature-independent paramagnetism (from 890 to 2191 × 10-6\documentclass{article}\pagestyle{empty}\begin{document}$ \frac{{{\rm emu}}}{{{\rm mol}}} $\end{document} per cluster). Thus, a single condensed octahedron carries roughly 440 × 10-6\documentclass{article}\pagestyle{empty}\begin{document}$ \frac{{{\rm emu}}}{{{\rm mol}}} $\end{document} as a temperature-independent paramagnetism, similar to the M6X17 halide clusters. In11Mo40O62 shows an interesting change in the temperature dependence of its magnetic suszeptibility.
    Notes: In3Mo11O17 besitzt ein Molybdatgerüst Mo22O348-, das zur allgemeinen Reihe Mo4n+2O6n+4x- (mit n = 5) gehört. Die in sternförmigen Kristallaggregaten wachsende Phase kristallisiert im orthorhombischen System (a = 988,0(2) pm, b = 951,2(2) pm, c = 3 176,7(4) pm). Es liegen oligomere Cluster aus fünf trans-kantenverknüpften Mo6-Oktaedern vor, die nach dem Verknüpfungsprinzip Mo22O18iO4/2i-iO28/2i-a über allen freien Kanten von O-Atomen umgeben sind. Im verbleibenden Hohlraum liegt ein In68+-Polykation, das vollständig dem entsprechenden Polykation aus In11Mo40O62 gleicht. Auch für die Mo - O- und Mo - Mo-Abstände innerhalb des Clusters werden gleiche Werte wie in In11Mo40O62 erreicht, doch gibt es in In3Mo11O17 mit 306 pm kürzere inter-Cluster-Abstände. In der Struktur treten Fehlordnungen auf, die mit dem Vorliegen von Konstitutionsisomeren interpretiert werden.Während der elektrische Widerstand von PbMo5O8 dem eines stark gestörten Metalls ähnelt (mit lokalem Minimum bei ca. 120 K), ist Tl0,8Sn0,6Mo7O11 aufgrund der Temperaturcharakteristik ein Halbleiter. Oxomolybdate mit längeren Oligomeren wie In11Mo40O62 und In3Mo11O17 zeigen metallische Leitfähigkeit. Dieser Gang korrespondiert mit der Größe der Cluster und ihrer elektronischen Kopplung untereinander, die in der Länge der inter-Cluster-Abstände zum Ausdruck kommt.Mit wachsender Clustergröße steigen sowohl das effektive magnetische Moment von 0,97 μB (PbMo5O8) auf 1,40 m̈B (In11Mo40O62) pro Cluster (Ausnahme: In3Mo11O17) als auch der Anteil des temperaturunabhängigen paramagnetischen Beitrags von 890 auf 2 191 × 10-6 \documentclass{article}\pagestyle{empty}\begin{document}$ \frac{{{\rm emu}}}{{{\rm mol}}} $\end{document} pro Cluster stetig an. Ein kondensierter Oktaeder hat daher einen Beitrag von 440 × 10-6\documentclass{article}\pagestyle{empty}\begin{document}$ \frac{{{\rm emu}}}{{{\rm mol}}} $\end{document} wie bei entsprechenden M6X12-Halogenidclustern. In11Mo40O62 zeigt einen auffälligen Wechsel im Temperaturverhalten der magnetischen Suszeptibilität.
    Additional Material: 7 Ill.
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    Koordinationszahl 4 oder 6 für Lithium??: Die Kristallstruktur von wasserfreiem Lithiumpermanganat, Li[MnO4] (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1419-1425 
    Details
    ISSN: 0044-2313
    Keywords: Lithium permanganate, Li[MnO4] ; preparation ; crystal structure ; neutron powder data ; MAPLE calculation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Coordination Number 4 or 6 for Lithium?: The Crystal Structure of Lithium Permanganate, Li[MnO4]Waterless 7Li[MnO4] was obtained by dehydration of 7Li[MnO4] · 3 D2O at 60°C above P4O10 in vacuum as violet powder.The structure determination by neutron diffraction measurements via pulsed polychromatic neutron source [time-of-flight powder diffractometer; profile-R-value = 2.1%, Bragg-R-value = 7.4%] confirms the space group Cmcm with a = 551.402(8), b = 839.754(15), c = 635.911(10) pm (Z = 4); parameters see text. The crystal structure of Li[MnO4] corresponds to the CrVO4-type with coordination number 6 for lithium and 4 for manganese.The Madelung Part of Lattice Energie, MAPLE, the Effective Coordination Numbers, ECoN and the charge distribution were calculated and discussed.
    Notes: Durch Trocknung von 7Li[MnO4] · 3 D2O bei 60°C über P4O10 im Vakuum wurde wasserfreies 7Li[MnO4] als violettes Pulver erhalten.Die Strukturaufklärung mittels Neutronenbeugungsmessungen im gepulsten polychromatischen Neutronenstrahl [Flugzeitdiffraktometer; Profil-R-Wert = 2,1%, Bragg-R-Wert = 7,4%] belegt die Raumgruppe Cmcm mit a = 551,402(8), b = 839,754(15), c = 635,911(10)pm (Z = 4); Parameter siehe Text. Die Kristallstruktur von Li[MnO4] entspricht dem CrVO4-Typ mit der Koordinationszahl 6 für Lithium und 4 für Mangan.Der Madelunganteil der Gitterenergie, MAPLE, Effektive Koordinationszahlen, ECoN und die Ladungsverteilung wurden berechnet und diskutiert.
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    Zur Kristallstruktur von MnF3 und MnPtF6 (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1426-1430 
    Details
    ISSN: 0044-2313
    Keywords: Manganese fluorides ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Crystal Structure of MnF3 and MnPtF6Single crystal investigations of MnF3 (rubyred) confirmed the crystal structure based on powder data [2]: monoclinic, space group C 2/c-C2h6 (No. 15) with a = 892.02 pm, b = 504.72 pm, c = 1 347.48 pm, β = 92.64° with Z = 12.The corresponding determination of the crystal structure of MnPtF6, yellow, confirmed the unit cell [3] with a = 510.47 pm, c = 1 421.0 pm and γ = 120°, Z = 3 space group R 3-C3i2 (No. 148).For both compounds detailed parameters respectively interatomic distances have been obtained.
    Notes: Einkristalluntersuchungen an MnF3 (rubinrot) bestätigen den aus Pulverdaten [2] abgeleiteten Strukturvorschlag: monoklin, Raumgruppe C 2/c-C2h6 (Nr. 15) mit a = 892,02 pm, b = 504,72 pm, c = 1 347,48 pm, β = 92,64° mit Z = 12 (Vierkreisdiffraktometerdaten).Entsprechende Einkristalluntersuchungen an MnPtF6, hellgelb, bestätigen auch hier die Abmessungen der Elementarzelle [3] mit a = 510,47 pm, c = 1 421,0 pm und γ = 120°, Z = 3 in der Raumgruppe R °3-C3i2 (Nr. 148). Für beide Verbindungen konnten damit genaue Parameter bzw. interatomare Abstände ermittelt werden.
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    Fluoroplatinate(IV) der Lanthaniden LnF[PtF6]. (Ln = Pr, Sm, Gd, Tb, Dy, Ho, Er) (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1431-1440 
    Details
    ISSN: 0044-2313
    Keywords: Fluoroplatinates(IV) ; preparation ; single crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Fluoroplatinates(IV) of the Lanthanides LnF[PtF6] (Ln = Pr, Sm, Gd, Tb, Dy, Ho, Er)For the first time fluorides LnF[PtF6] (Ln = Pr, Sm, Gd, Tb, Dy, Ho, Er), all yellow have been obtained. From single crystal data they crystallize monoclinic, space group P21/n-C2h5 (No. 14), Z = 4, Pr: a = 1 125.77(19) pm, b = 559.04(7) pm, c = 910.27(17) pm, β = 107.29(1)°; Sm: a = 1 114.63(31) pm, b = 552.70(12) pm, c = 898.02(20) pm, β = 107.24(2)°; Gd: a = 1 112.12(15) pm, b = 551.22(7) pm, c = 891.99(11) pm, β = 107.09(1)°; Tb (Powder data): a = 1 108.88(20) pm, b = 552.71(9) pm, c = 889.56(16) pm, β = 107.30(1)°; Dy: a = 1 100.28(23) pm, b = 547.77(8) pm, c = 882.41(13) pm, β = 107.32(1); Ho: a = 1 099.11(16) pm, b = 546.16(7) pm, c = 879.45(15) pm, β = 107.34(1)°; Er: a = 1 095.10(16) pm, b = 544.82(10) pm, c = 874.85(14) pm, β = 107.37(1)°.
    Notes: Erstmals dargestellt wurden Fluoride LnF[PtF6] (Ln = Pr, Sm, Gd, Tb, Dy, Ho, Er), alle gelb. Nach Einkristalluntersuchungen kristallisieren diese monoklin in der Raumgruppe P21/n-C2h5 (Nr. 14), Z = 4, Pr: a = 1 125,77(19) pm, b = 559,04(7) pm, c = 910,27(17) pm, β = 107,29(1)°; Sm: a = 1 114,63(31) pm, b = 552,70(12) pm, c = 898,02(20) pm, β = 107,24(2)°; Gd: a = 1 112,12(15) pm, b = 551,22(7) pm, c = 891,99(11) pm, β = 107,09(1)°; Tb (Pulverdaten): a = 1 108,88(20) pm, b = 552,71(9) pm, c = 889,56(16) pm, β = 107,30(1)°; Dy: 1 100,28(23) pm, b = 547,77(8) pm, c = 882,41(13) pm, β = 107,32(1)°; Ho: a = 1 099,11(16) pm, b = 546,16(7) pm, c = 879,45(15) pm, β = 107,34(1)°; Er: a = 1 095,10(16) pm, b = 544,82(10) pm, c = 874,85(14) pm, β = 107,37(1)°. Im Gegensatz zu älteren Befunden liegt die Raumgruppe P21/n-C2h5 (Nr. 14) mit einem verdoppelten Zellvolumen vor.
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    Ag3BiO3 und Ag5BiO4, die ersten Silberoxobismutate(III) (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1446-1454 
    Details
    ISSN: 0044-2313
    Keywords: Silver bismuthate ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ag3BiO3 and Ag5BiO4,the first Silver Oxobismuthates(III)Applying high oxygen pressures (100 MPa) Ag3BiO3 and Ag5BiO4 were prepared for the first time by reacting the binary components Ag2O and Bi2O3 at temperatures between 770 and 800 K. Single crystals of both compounds were grown hydrothermally from Ag2O and Bi2O3 at 620 K and at oxygen pressures of 10 MPa. The crystal structure determination (Ag3BiO3: I41, a = 14.1924(1), c = 8.7997(1) Å, Z = 16, 1 729 diffractometer data, Rw = 0.057; Ag5BiO4: P21/n, a = 5.855(1), b = 8.984(1), c = 12.457(1) Å, β = 91.49(1)Å, Z = 4, 2716 diffractometer data, Rw = 0.036) shows that in Ag5BiO4 bismuth approximately has a square pyramidal coordination by five oxygen atoms. Two such pyramids share an edge thus forming ‘isolated’ Bi2O810- anions. In Ag3BiO3 the same groups are linked by the terminal oxygen atoms to form a three dimensional network. In both structures the cation arrangements form variants of the Laves-phases MgCu2 with silver occupying the copper positions. The Mg positions are ordered occupied by bismuth and silver.
    Notes: Ag3BiO3 und Ag5BiO4 wurden durch Festkörperreaktion aus den binären Komponenten Ag2O und Bi2O3 bei Temperaturen zwischen 770 und 800 K und Sauerstoffdrücken von 100 MPa erstmals dargestellt. Einkristalle von beiden Verbindungen konnten durch Hydrothermalreaktion zwischen Ag2O und Bi2O3 bei 620 K unter einem Sauerstoffdruck von 10 MPa dargestellt werden. Nach den Ergebnissen der Röntgenstrukturanalyse (Ag3BiO3: I41, a = 14,1924(1), c = 8,7997(1) Å, Z = 16, 1 729 Diffraktometerdaten, Rw = 0,057; Ag5BiO4: P21/n, a = 5,855(1), b = 8,984(1), c = 12,457(1) Å, β = 91,49(1)Å, Z = 4, 2716 Diffraktometerdaten, Rw = 0,036) liegt in Ag5BiO4 eine transständige Verknüpfung von quadratisch-pyramidal mit Sauerstoff koordinierten BiO5-Baueinheiten zu dimeren, ‘isolierten’, Bi2O810--Gruppen vor. In Ag3BiO3 findet man die gleichen Bi2O8-Baugruppen, die hier jedoch dreidimensional über die terminalen Sauerstoffatome verknüpft sind. In beiden Verbindungen sind die Kationen analog zur Laves-Phase MgCu2 angeordnet mit gemischter Besetzung der Mg-Position durch Silber und Bismut sowie Besetzung der Cu-Positionen ausschließlich durch Silber.
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    Synthese und Molekülstruktur von Barium-bis[N,N′-bis(trimethylsilyl)benzamidinat] · DME · THF (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1455-1461 
    Details
    ISSN: 0044-2313
    Keywords: Barium-bis[N,N′-bis(trimethylsilyl)benzamidinate] · DME · THF ; Benzamidinate ; X-ray Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Molecular Structure of Barium Bis[N,N′-bis(trimethylsilyl)benzamidinate] ° DME ° THFBarium bis[N,N′-bis(trimethylsilyl)benzamidinate] · thf · dme crystallizes in the monoclinic space group P21/n with a = 1 122.0(2), b = 2 190.7(4), c = 1 840.2(3) pm, β = 98.04(1)° and Z = 4 containing a metal center in a distorted monocapped trigonal prismatic surrounding. The barium dibenzamidinate moiety is sent with an angle of 120°, although this leads to different Ba—N distances of 273 and 282 pm originating from the interligand repulsion of the trimethylsilyl groups and the dme substituent. The 1,3-diazaallyl fragment with C—N bond lengths of 132 pm shows a delocalisation of the anionic charge.
    Notes: Barium-bis[N,N′-bis(trimethylsilyl)-benzamidinat] · DME · THF kristallisiert in der monoklinen Raumgruppe P21/n mit a = 1 122,0(2), b = 2 190,7(4), c = 1 840,2(3) pm, β = 98,04(1)° und Z = 4 mit einem Metallzentrum in einer einfach überdachten, verzerrt prismatischen Umgebung. Die Barium-dibenzamidinat-Substruktur ist mit einem Winkel von 120° gewinkelt, die zwei jeweils verschiedenen Ba—N-Abstände von 273 und 282 pm rühren von der sterischen Hinderung zwischen den Trimethylsilyl-Gruppen und dem DME-Liganden her. Das 1,3-Diazaallyl-Fragment weist mit C—N-Bindungslängen von 132 pm eine Delokalisation der anionischen Ladung auf.
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    Polysulfonylamine. XLII. Ein Aquasilber(I)-Komplex mit einem Ag(m̈-H2O)2Ag-Strukturmotiv: Röntgenstrukturanalytische und thermoanalytische Charakterisierung von Aqua(1,1,3,3-tetraoxo-1,3,2-benzodithiazolido)silber(I) (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1441-1445 
    Details
    ISSN: 0044-2313
    Keywords: Disulfonyl amines ; silver(I) 1,1,3,3-tetraoxo-1,3,2-benzodithiazolide ; aqua(1,1,3,3-tetraoxo-1,3,2-benzodithiazolido)silver(I) ; crystal structure ; thermal analysis ; calorimetry ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polysulfonyl Amines. XLII. An Aquasilver(I) Complex with an Ag(m̈-H2O)2Ag Structural Unit: Characterization of Aqua(1,1,3,3-tetraoxo-1,3,2-benzodithiazolido)silver(I) by X-Ray Diffractometry and Thermal AnalysisThe title compound C6H4(SO2)2NAg · H2O, where C6H4(SO2)2Nº is the anion of 1,2-benzenedisulfonimide, crystallizes in the monoclinic space group C2/m with (at -95°C) a = 1 129,7(3), b = 1 196.1(3), c = 810.7(2) pm, β = 124.25(2)°, V = 0.9055 nm3, Z = 4, Dx = 2.524 Mg m-3. The crystal packing consists of [Ag(m̈-H2O)2Ag{m̈-C6H4(SO2)2N}2]n bands with crystallographic mirror symmetry, associated into layers by H-bonds with O(W) - O(S) 289.7 pm. The Ag(m̈-H2O)2Ag moiety forms a planar four-membered ring with Ag—O(W)—Ag 97.3°, O(W)—Ag—O(W) 82.7° and Ag°Ag 372.1 pm. In the Ag{C6H4(SO2)2N}2Ag′ unit, the anions act as tridentate (N, 1-O, 3-O)-ligands: One is N-bonded to Ag and O,O-chelated to Ag′, the other N-bonded to Ag′ and O,O-chelated to Ag. The silver atoms are (O4N)-pentacoordinate, with nitrogen in the apical position of a distorted square pyramid [Ag—N 223.6, Ag—O(W) 247.8, Ag—O(S) 259.4 pm]. The thermochemical behaviour of the hydrate was investigated by thermal analysis and calorimetry. Water is only released at temperatures above 220°C. The dehydration enthalpy at 298 K is + 13.9 kJ mol-1.
    Notes: Die Titelverbindung C6H4(SO2)2NAg · H2O, mit C6H4(SO2)2N- = Anion des 1,2-Benzoldisulfonsäureimids, kristallisiert in der monoklinen Raumgruppe C2/m mit (bei -95°C) a = 1 129,7(3), b = 1 196,1(3), c = 810,7(2) pm, β = 124,25(2)°, V = 0,9055 nm3, Z = 4, Dx = 2,524 Mg m-3. Die Kristallpackung besteht aus Strängen des Typs [Ag(m̈-H2O)2Ag{m̈-C6H4(SO2)2N}2]n mit kristallographischer Spiegelsymmetrie, die über H-Brücken mit O(W)…O(S) 289,7 pm zu Schichten assoziiert sind. Die Ag(m̈—H2O)2Ag-Einheit bildet einen planaren Vierring mit Ag - O(W) - Ag 97,3°, O(W) - Ag - O(W) 82,7° und Ag…Ag 372,1 pm. In der Ag{m̈—C6H4(SO2)2N}2Ag′-Einheit wirken die Anionen als dreizähnige (N, 1-O, 3-O)-Liganden, und zwar das eine als N-Donor gegenüber Ag und als O,O-Chelatligand gegenüber Ag′, das andere umgekehrt als N-Donor gegenüber Ag′ und als O,O-Chelatligand gegenüber Ag. Die Silberatome sind (O4N)-pentakoordiniert mit dem Stickstoffatom am Scheitelpunkt einer verzerrten quadratischen Pyramide [Ag—N 223,6, Ag—O(W) 247,8, Ag—O(S) 259,4 pm]. Das thermochemische Verhalten des Hydrats wurde mit thermoanalytischen und kalorimetrischen Methoden untersucht. Das Wasser wird erst bei Temperaturen oberhalb 220°C abgegeben. Die Dehydratationsenthalpie bei 298 K beträgt + 13,9 kJ mol-1.
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    Kristallstruktur von Caesiumacetat, Cs(CH3COO) (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1462-1464 
    Details
    ISSN: 0044-2313
    Keywords: Cesium Acetate ; Synthesis ; Crystal Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal Structure of Cesium Acetate, Cs(CH3COO).The crystal structure of cesium acetate, Cs(CH3COO), was determined from single crystal fourcirclediffractometer data: hexagonal crystal system, P6/m (No. 175), Z = 6, a = 1 488.0(2), c = 397.65(5) pm, Vm = 76.54(2) cm3/mol, R = 0.045, Rw = 0.030. The structure consists of flat layers of acetate anions parallel (001) that are separated by layers of cesium cations. There is a close relationship with the CaF2 type according to CsO2(CCH3): each cesium cation has eight oxygen atoms as nearest neighbours. They form a heavily distorted cube with trapezoidal basal faces. In contrast to CaF2, these polyhedra are linked via three faces and two edges to a three-dimensional network.
    Notes: Die Kristallstruktur von wasserfreiem Caesiumacetat, Cs(CH3COO), wurde anhand von Vierkreisdiffraktometerdaten bestimmt: hexagonales Kristallsystem, P6/m (Nr. 175), Z = 6, a = 1 488,0(2), c = 397,65(5) pm, Vm = 76,54(2) cm3/mol, R = 0,045, Rw = 0,030. Die Struktur besteht aus ebenen Schichten von Acetationen parallel (001), die durch Caesium-Schichten separiert sind. Es besteht eine enge Verwandtschaft zum CaF2-Typ gemäß CsO2(CCH3): die Cs+-Ionen sind von 8 Sauerstoffatomen in Form eines stark verzerrten Würfels mit trapezoiden Grundflächen umgeben. Im Unterschied zu CaF2 sind die Würfel jedoch nur über drei gemeinsame Flächen und zwei Kanten zu einem dreidimensionalen Netzwerk verknüpft.
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    Supermesityl-stabilisierte Iminoborane. III (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1474-1478 
    Details
    ISSN: 0044-2313
    Keywords: 2,4,6-Tri-t-butylphenyl-substituted iminoboranes ; thermal condensation ; benzo[1]borolanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Supermesityl stabilized Iminoboranes. IIINew Iminoboranes R—B=N—R′ (R = 2,4,6(t-Bu)3C6H2), IIa-IIf, were obtained by base-induced HF-elimination from RBF—NHR′ (Ia-Ie) or directly from RBF2 and lithiated H2NR′ (for IIf). Compounds II exhibit a differentiated behaviour upon thermal treatment depending on R′. While IIa (R′ = H) immediately reacts to give the corresponding benzo[1]borolane IIIa, the dimeric diazadiboretidine is formed from IIb (R′ = Me) at 100°C; IIc (R = Et) and IId (R = C6H5) deliver the benzo[1]borolanes IIIc and IIId when they are heated to 180°C (in melt). IIe (R = 2,6(i-Pr)C6H3) and IIf (R = adamantyl) are stable at 250°C. All compounds were characterized by elemental analyses and spectroscopically (MS, IR, NMR: 1H, 13C, 11B, 19F and in part 15N).
    Notes: Neue Iminoborane R—B=N—R′ (R = 2,4,6(t-Bu)3C6H2), IIa-IIf, wurden durch baseninduzierte HF-Eliminierung aus RBF—NHR′ (Ia-Ie) oder direkt aus RBF2 und lithiiertem H2NR′ (für IIf) erhalten. Die Verbindungen von Typ II zeigen in Abhängigkeit von R′ ein ausgeprägt differenziertes Verhalten bei thermischer Belastung. Während IIa (R′ = H) sofort zum entsprechenden Benzo[1]borolan IIIa weiterreagiert, ergibt IIb (R′ = Me) bei 100°C das dimere Diazadiboretidin IVb, während IIc (R = Et) und IId (R — C6H5) erst als Schmelze bei 180°C zu den Benzo[1]borolanen IIIc und IIId reagieren. IIe (R = Adamantyl) und IIf (R = 2,6-(i-Pr)2C6H3) sind bei 250°C stabil. Alle Verbindungen wurden elementaranalytisch und spektroskopisch (MS, IR, NMR: 1H, 13C, 11B, 19F und teilweise 15N) charakterisiert.
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    Synthese funktionell substituierter Disilane auf der Basis von Triflatderivaten (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1479-1482 
    Details
    ISSN: 0044-2313
    Keywords: Silyltriflates ; chlorosilanes ; oligosilanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of Functional Substituted Disilanes on the Basis of Triflate DerivativesFunctional substituted disilanes are prepared by reaction of phenylated disilanes with trifuloromethanesulfonic acid. Reduction of the triflate derivatives with LiAlH4 leads to Si—H substituted disilanes. The chlorinated disilanes are obtained by reaction of the triflate derivatives with Et3NHCl. Chloro-hydrogen substituted disilanes are prepared by combination of both reaction types. The preparation of these compounds in a high purity is difficult on other ways.
    Notes: Funktionell substituierte Disilane werden durch Umsetzung phenylierter Disilane mit Trifluormethansulfonsäure erhalten. Die Reduktion der Triflatderivate mit LiAlH4 führt zu den Si—H-substituierten Disilanen, die Umsetzung mit Et3NHCl ergibt die chlorierten Vertreter. Durch gezielte Kombination beider Reaktionstypen gelingt die Synthese von Chlor - Wasserstoff-Disilanen mit Substitutionsmustern, die in reiner Form auf anderen Wegen nicht oder nur unter großem präparativen Aufwand darstellbar sind.
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    Untersuchungen an Polyhalogeniden. XI. Darstellung und Kristallstruktur des Diethylmethylphenylammoniumtriiodids, Et2MePhNI3 (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1483-1487 
    Details
    ISSN: 0044-2313
    Keywords: Crystal structure ; polyiodide ; triiodide ; tetraorganylammonium ion ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Studies on Polyhalides. 11 Preparation and Crystal Structure of Diethylmethylphenylammoniumtriiodide, Et2MePhNI3Diethylmethylphenylammoniumtriiodide C11H18NI3 crystallizes at room temperature monoclinically with a = 824.1(2) pm, b = 1 428.5(2) pm, c = 1 430.0(2) pm, β = 103.17(3)° and Z = 4.The crystal structure is build up from layers of the quarternary ammonium ions Et2MePhN+ and of the triiodide ions I3-, which alternate with each other along [1 0 0]. The packing of these layers and of the groups within each layer seems to be particularly effective without forming noticeable short contact distances.
    Notes: Diethylmethylphenylammoniumtriiodid C11H18NI3 kristallisiert bei Raumtemperatur in der monoklinen Raumgruppe P21/c mit a = 824,1(2) pm, b = 1 428,5(2) pm, c = 1 430,0(2) pm, β = 103,17(3)° und Z = 4.Die Kristallstruktur wird aus Schichten der quartären Ammoniumionen Et2MePhN+ und aus solchen der Triiodidionen I3- aufgebaut, die sich längs [1 0 0] abwechseln. Die Packung dieser Schichten und der Baugruppen innerhalb jeder Schicht erscheint ohne Knüpfung besonderer kurzer Kontakte bemerkenswert günstig.
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    Ternäre Acetate der Lanthanide mit Caesium: Dimere und Trimere in CsLu(CH3COO)4 bzw. Cs2[Lu3(CH3COO)10(OH)(H2O)]. Synthese, Kristallstrukturen und Thermolyse (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1465-1473 
    Details
    ISSN: 0044-2313
    Keywords: Cesium Lutetium(III) Acetate ; Synthesis ; Crystal Structure ; Thermolysis ; Evolved Gas Aalysis (EGA) ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ternary Acetates of the Lanthanides with Cesium: Dimers in CsLu(CH3COO)4 and Trimers in Cs2[Lu3(CH3COO)10(OH)(H2O)]. Synthesis, Crystal Structures, ThermolysisSingle crystals of CsLu(CH3COO)4 and Cs2[Lu3(CH3COO)10(OH)(H2O)] were obtained from an aqueous solution of lutetium and cesium acetate in a 1:1 molar ratio. The crystal structures (CsLu(CH3COO)4: monoclinic, P21/n (no. 14), Z = 8, a = 1 293.1(2), b = 1 323.8(2), c = 1 622.5(3) pm, β = 92.01(2)°, Vm = 208.97(6) cm3/mol, R = 0.056, Rw = 0.034; Cs2[Lu3(CH3COO)10(OH)(H2O)]: monoclinic, C2/c (no.15), Z = 4, a = 2 138.5(6), b = 1 378.0(3), C = 1 482.9(4) pm, β = 106.15(2)°, Vm = 632.0(3) cm3/mol, R = 0.049, Rw = 0.036) were determined from four-circle-diffractometer data. The structures consist of dimers and trimers, respectively, that are built by bridging acetate groups. These units are fragments of the infinite chains of the Ho(CH3COO)3 type of structure. The isotypic compounds CsM(CH3COO)4 with M=Eu—Lu were synthesized and characterized by the X-ray Guinier technique. The thermal decomposition of CsLu(CH3COO)4 was examined with thermoanalytical methods (TG/DSC with coupled gas analysis) and the Guinier-Simon technique: it decomposes at 260°C in an endothermic reaction to Lu2O3 and Cs2CO3.
    Notes: Die Verbindungen CsLu(CH3COO)4 und Cs2[Lu3(CH3COO)10(OH)(H2O)] konnten aus wäßriger Lösung von Cs(CH3COO) und Lu(CH3COO)10 (OH)(H2O) dargestellt werden. Ihre Kristallstrukturen (CsLu(CH3COO)4: monoklin, P21/n (Nr. 14), Z = 8, a = 1293,1(2), b = 1323,8(2), c = 1 622,5(3) pm, β = 92,01(2)°, Vm = 208,97(6) cm3/mol, R = 0,056, Rw = 0,034; Cs2[Lu3(CH3COO)10(OH)(H2O)]: monoklin, C2/c (Nr. 15), Z = 4, a = 2138,5(6), b = 1378,0(3), C = 1 482,9(4) pm, β = 106,15(2)°, Vm = 632,0(3) cm3/mol, R = 0,049, Rw = 0,036) wurden anhand von Vierkreisdiffraktometerdaten bestimmt. In den Kristallstrukturen liegen zwei- bzw. dreikernige Baueinheiten vor, die durch verbrückende Acetatgruppen aufgebaut werden und Fragmente der unendlichen Ketten im Ho(CH3COO)3-Typ darstellen. Die isotypen Verbindungen CsM(CH3COO)4, M=Eu—Lu, wurden hergestellt und mittels Pulver-Röntgenmethoden charakterisiert. Das thermische Verhalten von CsLu(CH3COO)4 wurde mittels TG/DSC und simultaner Gasanalyse (EGA) einerseits und mit Hilfe der Guinier-Simon-Technik andererseits untersucht: Es zersetzt sich ab 260°C in Cs2CO3 und Lu2O3.
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    Masthead (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993) 
    Details
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Intramolekulare C—H-Aktivierung bei der Reaktion von Bis(benzylcyclopentadienyl)zirconiumdichlorid mit Vinyllithium  -  Bildung eines Crotyl-zirconacyclus (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1488-1490 
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    ISSN: 0044-2313
    Keywords: Bis(benzylcyclopentadienyl)zirconium dichloride ; C—H Activation ; Orthometallation Reaction ; Crotylzirconium Compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Intramolecular C—H Activation at Reaction of Bis(benzylcyclopentadienyl)zirconium Dichloride with Vinyllithium  -  Formation of a Crotyl ZirconacyclusBis(benzylcyclopentadienyl)zirconium dichloride, (C6H5CH2—C5H4)2ZrCl2 (V), reacts with vinyl lithium with formation of the chiral compound (C6H5CH2—C5H4)— —CH2CH=CHCH3 (IX) as the product of vinyl group coupling and an orthometallation reaction. The reaction mechanism and the 13C n.m.r. spectrum are discussed.
    Notes: Bei der Reaktion von Bis(benzylcyclopentadienyl)zirconiumdichlorid, (C6H5CH2—C5H4)2ZrCl2 (V), mit Vinyllithium entsteht nicht das entsprechende Divinylderivat, sondern die chirale Crotylverbindung der Formel (C6H5CH2—C5H4)— —CH2CH=CHCH3 (IX) als Produkt einer Kopplung von Vinylgruppen und einer Orthometallierungsreaktion. Der Bildungsmechanismus und das 13C-NMR-Spektrum werden diskutiert.
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    Bildung siliciumorganischer Verbindungen. 109. Reaktionen vollhydrierter Carbosilane mit LithiumalkylenProfessor Ulrich Wannagat zum 70. Geburtstage gewidmet (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1491-1493 
    Details
    ISSN: 0044-2313
    Keywords: Reactions of Perhydrogenated Carbosilanes with Alkyl-Lithium ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Formation of Organosilicon Compounds. 109. Reactions of Perhydrogenated Carbosilanes with Alkyl-Lithium CompoundsSi-hydrogenated linear carbosilanes react with MeLi or nBuLi to give the Si-alkylated derivatives. In contrast to the Si-methylated derivatives of (H3Si—CH2)2SiH2 1 and (H3Si)2CH2 2 and to (Me2Si—CH2)3 no lithiation of CH2 groups is observed. Such, 1 with nBuLi yields nBuH2Si—CH2—SiH2—CH2—SiH3 5 and (nBuH2Si—CH2)2SiH2 6. 2 reacts with nBuLi to give nBuH2Si—CH2SiH3 7 and (nBuH2Si)2CH2 8 besides of 1, 5 und 6. The latter results from a cleavage of a Si—C bond in 2 Producing nBuSiH3 and LiCH2—SiH3 which combines with 2 to 1. Subsequently 1 forms 5 and 6. No higher alkylated derivatives of 1 or 2 could be detected.
    Notes: Si-hydrierte, lineare Carbosilane reagieren mit MeLi bzw. nBuLi unter Alkylierung der SiH- und nicht unter Lithiierung der CH2-Gruppen, wie sie von den Si-methylierten Derivaten von (H3Si—CH2)2SiH2 1, (H3Si)2CH2 2 und (Me2Si—CH2)3 bekannt sind. 1 bildet mit nBuLi H3Si—CH2—SiH2—CH2—SiH2nBu 5 und (nBuH2Si—CH2)2—SiH2 6. Die Umsetzung von 2 führt zu H3Si—CH2—SiH2nBu 7 und (nBuH2Si)2CH2 8 neben den Verbindungen 1, 5 und 6. Diese sind auf die Spaltung der Si—C-Bindung in 2 zurückzuführen (Bildung von nBuSiH3 und LiCH2—SiH3). LiCH2—SiH3 reagiert mit 2 zu 1 und diese mit nBuLi weiter zu 5 und 6. Höheralkylierte Derivate von 1 und 2 werden nicht beobachtet. Es erfolgt keine Lithiierung der CH2-Gruppe.
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    Einfluß von Ringgröße und Substitution auf die oxidative Addition cyclischer Carbonsäureanhydride und -imide an den Rumpf (N N)Niº (N N = α, α′-Dipyridyl, Tetramethylethylendiamin)Professor Heinrich Nöth zum 65. Geburtstage gewidmet (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1512-1518 
    Details
    ISSN: 0044-2313
    Keywords: Nickel complexes ; nickelacyclic complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Influence of Ring Size and Substitution on the Oxidative Addition of Cyclic Carboxylic Acid Anhydrides and Imides to the Moiety (N N)Niº (N N = bipy, tetramethylethylenediamine)(dipy)(COD) or a mixture of tmed/Ni(COD)2 easily react with cyclic carboxylic acid anhydrides by an oxidative addition. After decarbonylation with succinic acid anhydride a five-membered, with glutaric acid anhydride a six-membered metallacycle are formed - or With diphenic acid anhydride we obtained a seven-membered chelate in the boat form (XIV). Along their bond axis the two aromatic rings are twisted by 127°, i.e. the conjugative interaction is weak.Itaconic acid anhydride, as a polar olefine, can coordinate to the moiety (tmed)Ni side-on. But also on oxidative addition, yielding the five-membered chelate (XVI), is possible. The five-membered chelate is the only Product of the reaction with (dipy)Ni(COD).1.8-naphthalic acid anhydride (NSA), because of its rigidity, is not suitable for an oxidative addition to electron-rich nickel(O) complexes. But as a π acceptor ligand with a relatively low half wave potential NSA displaces COD of (dipy)Ni(COD) forming (dipy)Ni(NSA) · 0.25 THF (XVIII). One of the final products of the acidolysis of [(dipy)Ni]2(PPI) · 1.5 THF (XIX PPI=N-phenyl phthalimide) is benzanilide, a compound which might be an indicator of an oxidative additive connected with an -bond breaking in the course of the synthesis of XIX. But ir-data shows the framework of PPI to be preserved in the complex XIX. Evidently the bond breaking proceeds in the course of the acidolysis.
    Notes: (dipy)Ni(COD) bzw. ein Gemisch von tmed/Ni(COD)2 reagieren mit cyclischen Carbonsäure-anhydriden unter oxidativer Addition. Nach Decarbonylierung entstehen dabei mit Bernsteinsäureanhydrid ein fünfgliedriger, mit Glutarsäureanhydrid ein sechsgliedriger Nickelacyclus bzw. Mit Diphensäureanhydrid erhielten wir ein siebengliedriges Chelat in der Wannenform (XIV). Die beiden aromatischen Ringsysteme von XIV sind entlang der Bindungsachse um 127° gegeneinander verdrillt. Die konjugative Wechselwirkung zwischen diesen Ringen bleibt daher gering.Itaconsäureanhydrid kann an dem Rumpf (tmed)Ni als polares Olefin und damit side-on koordinieren. Es ist aber auch eine oxidative Addition unter Bildung von (XVI) möglich. Ausschließlich das oxidative Additionsprodukt wird bei der Umsetzung mit (dipy)Ni(COD) erhalten.Naphthalsäureanhydrid (NSA) mit seinem starren Hetero-Sechsring ist zu einer oxidativen Addition an elektronenreiche Nickel(0)-Komplexe nicht befähigt. Als π-Akzeptorligand mit einem relativ niedrigen ersten Halbstufenpotential vermag es jedoch COD aus (dipy)Ni(COD) unter Bildung von (dipy)Ni(NSA) 0,25 THF (XVIII) zu verdrängen.Die Acidolyse von [(dipy)Ni]2(PPI) · 1,5 THF (XIX; PPI = N-Phenylphthalimid) ergibt mit Benzanilid eine Verbindung, die auf eine bei der Synthese von XIX abgelaufene oxidative Addition unter -Bindungs-spaltung hindeutet. IR-Daten lassen jedoch nur den Schluß zu, daß im Komplex XIX das Skelett PPI noch erhalten ist. Die Bindungsspaltung erfolgt offenbar erst im Verlauf der Acidolyse.
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    Synthese, Eigenschaften und Struktur von oktamerem Titanimidchlorid [Ti(NSiMe3)Cl2]8Professor Heinrich Nöth zum 65. Geburtstage gewidmet (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1526-1529 
    Details
    ISSN: 0044-2313
    Keywords: Octameric titanium imide chloride, [Ti(NSiMe3)Cl2]8 ; synthesis ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis, Properties, and Structure of Octameric Titanium Imide Chloride [Ti(NSiMe3)Cl2]8The reaction of TiCl4 with N(SiMe3)3 in sealed glas-tubes yields the titanium imide chloride [Ti(NSiMe3)Cl2]8 (1). It crystallizes in the space group C2/c with a = 2 704.5(4), b = 1 303.9(1), c = 2 205.4(2) pm, β = 112.78(1)°, Z = 4. In 1 six Ti atoms are linked together by chloro and trimethylsilylimido bridges to form a ring structure. Two TiCl2-groups are bound in addition to the ring by two imido bridges. Upon annealing at 250°C 1 transformes to the isomeric polymer [Ti(NSiMe3)Cl2]n. Above 250°C 1 decomposes under separation of Me3SiCl affording TiNCl.
    Notes: TiCl4 reagiert in zugeschmolzenen Glasampullen mit N(SiMe3)3 zum Titanimidchlorid [Ti(NSiMe3)Cl2]8 (1). Es kristallisiert monoklin in der Raumgruppe C2/c mit a = 2 704,5(4), b = 1 303,9(1), c = 2 205,4(2) pm, β = 112,78(1)°, Z = 4. In 1 sind sechs Titanatome über Chloro- und Trimethylsilylimido-Brücken zu einer Ringstruktur verknüpft. Zusätzlich sind zwei TiCl2-Gruppen über zwei Imidobrücken an dß Ring gebunden. Durch Tempern bei 250°C wird 1 in das isomere Polymer [Ti(NSiMe3)Cl2]n umgewandelt. Oberhalb 250°C zersetzt sich 1 unter Abspaltung von Me3SiCl zu TiNCl.
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    Darstellung und Eigenschaften von Phosphanboranen polyfunktioneller Phosphanliganden; Kristallstrukturen des Bis(boranatodiphenylphosphonio)methans und des Tetrakis[(boranatodiphenylphosphonio)methyl]methansProfessor Heinrich Nöth zum 65. Geburtstage gewidmet (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1519-1525 
    Details
    ISSN: 0044-2313
    Keywords: Phosphane-boranes polyfunctional phosphane-boranes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Properties of Phosphane-Boranes Derived from Polyfunctional Phosphanes; Crystal Structures of Bis(boranatodiphenylphosphonio)methane and Tetrakis[(boranato-diphenylphosphonio)methyl]methaneBis(boranatodiphenylphosphonio)methane has been prepared in pure form from Ph2PCH2PPh2 (dppm) via two synthetic routes and its crystal structure determined. The molecule adopts a conformation very similar to that of the parent dppm ligand, which reflects the influences of the repulsive charges in the functional groups. Analogous phosphine-boranes were obtained from 1,1,1-tris(diphenylphosphinomethyl)ethane and tetrakis(diphenylphosphinomethyl)methane. The crystal structure has also been determined for the tetra-borylated derivative of the latter. A highly symmetrical arrangement has been found which corresponds to a relaxed conformation of the four dipolar groups. From C(CH2PPh2)4 and H2BBr · SMe2 an ionic, spirobicyclic Product was obtained, which resembles the monocyclic analogues previously described in its Properties and spectroscopic data.
    Notes: Bis(boranatodiphenylphosphonio)methan wurde aus Ph2PCH2PPh2 (dppm) nach zwei präparativen Verfahren in reiner Form dargestellt und seine Kristallstruktur bestimmt. Es wird eine Konformation gefunden, die nur wenig von der des freien dppm-Liganden abweicht, aber den veränderten repulsiven Ladungseinflüssen Rechnung trägt. Analoge Phosphan-borane wurden weiter hergestellt aus 1,1,1- Tris(diphenylphosphinomethyl)ethan und Tetrakis(diphenylphosphinomethyl)methan. Von dem von letzterem abgeleiteten vierfachen BH3-Komplex wurde ebenfalls die Kristallstruktur bestimmt. Es ergab sich die erwartete hochsymmetrische Molekülstruktur mit konformativ entspannter Anordnung der Funktionen. Aus C(CH2PPh2)4 wurde mit H2BBr · SMe2 ein ionisches, spirobicyclisches Produkt erhalten, das sich in seinen Eigenschaften und spektroskopischen Daten früher beschriebenen monocyclischen Analogen anschließt.
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    Bildung siliciumorganischer Verbindungen. 110. Reaktionen von (Cl3Si)2CCl2, seiner Si-methylierten Derivate, von (Cl3Si)2CHCl, (Cl3Si)2C(Cl)Me und Me2CCl2 mit Silicium (Cu-Kat.)Professor Heinrich Nöth zum 65. Geburtstage gewidmet (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1494-1511 
    Details
    ISSN: 0044-2313
    Keywords: Organosilicon compounds ; Cu-catalyzed reaction of silicon with bis(trichlorsilyl)dichlormethane and related compounds ; formation of Si-chlorinated trisila- and tetrasilamethanes, 2,4 disilacyclobutanes and C-spiro-linked Disilacyclopropanes ; crystal structure of 1,1,3,3-Tetrachlor-2,2,4,4-tetrakis(trichlorsilyl)- 1,3-disilacyclobutane (Si6C2Cl16) and 1,1,3,3,5,5,7,7-octachlor-2,2,6,6-tetrakis(trichlorsilyl)-1,3,5,7-tetrasilaspiro [3.3]-heptane (Si8C3Cl20) ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Formation of Organosilicon Compounds. 110. Reactions of (Cl3Si)2CCl2 and its Si-methylated Derivatives as well as of (Cl3Si)2CHCl, (Cl3Si)2C(Cl)Me and Me2CCl2 with Silicon (Cu cat.)The reactions of (Cl3Si)2CCl2 1, its Si-methylated derivatives (Me3Si)2CCl2 8, Me3Si—CCl2—SiMe2Cl 9, (ClMe2Si)2CCl2 10, Me3Si—CCl2—SiMeCl2 11, Cl2MeSi—CCl2—SiCl3 12 as well as of (Cl3Si)2CHCl 38, (Cl3Si)2CClMe 39 and of Me2CCl2 with Si (Cu cat.) in a fluid bed reactor (38 and 39 also in a stirred solid bedreactor) arc presented. While (Cl3Si)2CCl21yields C(SiCl3)4 2 the 1,1,3,3-tetrachloro-2,2,4,4-tetrakis(trichlorsilyl)-1,3-disilacyclobutane Si6C2Cl16 3 and the related C-spiro linked disilacyclobutanes Si8C3Cl20 4, Si10C4Cl24 5, Si12C5Cl28 6, Si14C6Cl32 7this type of compounds is not obtained starting from the Si-methylated derivatives 8, 9, 10, 11They Produce a number of variously Si-chlorinated and -methylated tetrasila- and trisilamethanes. However, Cl2MeSi—CCl2—SiCl3 12forms besides of Si-chlorinated trisilamethanes also the disilacyclobutanes Si6C2Cl15Me 34and cis- and trans Si6C2Cl14Me2 35 as well as the spiro-linked disilacyclobutanes Si8C3Cl19Me 36, Si8C3Cl18Me2 37. (Cl3Si)2CHCl 38 mainly yields HC(SiCl3)3 31and also the disilacyclobutanes cis- and trans-(Cl3Si)HC(SiCl2)2CH(SiCl3) 41and (Cl3Si)2C(SiCl2)2CH(SiCl3) 45the 1,3,5-trisilacyclohexane [Cl3Si(H)C—SiCl2]3 44 as well as [(Cl3Si)2CH]2SiCl2, and (Cl3Si)2CClMe 39 mainly yields (Cl3Si)2C=CH2and (Cl3Si)2besides of HC(SiCl3)3, MeC(SiCl3)3and (Cl3Si)3C—SiCl2Me.,. Me2CCl2 59 mainly yields Me(Cl)C=CH2, Me2CHCl and HCl2Si—CMe2—SiCl3, besides of Me2C(SiCl3)2 and Me2C(SiCl2H)2 Compound 3 crystallizes triclinically in the space group P1 (Nr. 2) mit a = 900,3, b = 914,0, c = 855,3 pm, α = 116,45°, β = 101,44°, γ = 95,86° and one molecule per unit cell. Compound 4 crystallizes monoclinically in thc space group C2/c (no. 15) with a = 3158.3,b = I 103.7, c = 2037.4 pm, β = 1 16.62° and 8 molecules pcr unit cell. The disilacyclobutane ring of compound 3 is plane, showing a mean distance of d(Si-C) =19 1.8 pm and the usual deformations of endocyclic angles: αSi = 94,2°〉 85,8° = αC.The spiro-linked disilacyclobutane rings of compound4 are slightly folded by a mean angle of (19.0°). Their mean distances were found to be d(Si—C) = 190.4 pm relating to the central carbon atom and 192.0 pm to the outer ones, respectively. The deformations of endocyclic angles: αSi = 93,9°〉 84,4° = αC are comparable to those of compound 3.
    Notes: Es wird über die Umsetzungen von (Cl3Si)2CCl2 1, seiner Si-methylierten Derivate (Me3Si)2CCl2 8, Me3Si—CCl2—SiMe2Cl 9, (ClMe2Si)2CCl2 10, Me3Si—CCl2—SiMeCl2 11, Cl2MeSi—CCl2—SiCl3 12 sowie von (Cl3Si)2CHCl 38, (Cl3Si)2CClMe 39 und Me2CCl2 mit Silicium (Cu-Kat.) in der Wirbelschicht bei 300°C - von 38 und 39 auch im Festbett - berichtet. Während die Umsetzung von (Cl3Si)2CCl2 zu C(SiCl3)4 2, dem 1,1,3,3-Tetrachlor-2,2,4,4-tetrakis(trichlorsilyl)-1,3-disilacyclobutan Si6C2Cl16 3 und den C-spiro-verbrückten Disilacyclobutanen Si8C3Cl20 4, Si10C4Cl24 5, Si12C5Cl28 6, Si14C6Cl32 7 führen, wird dieser Verbindungstyp von den Si-methylierten Verbindungen 8, 9, 10, 11 nicht gebildet. Ihre Umsetzungen führen zu unterschiedlich Si-chlorierten-methylierten Tetrasila- bzw. Trisilamethanen. Dagegen bildet das Cl2MeSi—CCl2—SiCl3 12 neben Si-chlorierten Trisilamethanen die Disilacyclobutane Si6C2Cl15Me 34, Si6C2Cl14Me2 35 (cis- und trans), 4 und Si8C3Cl19Me 36, Si8C3Cl18Me2 37. (Cl3Si)2CHCl 38 bildet HC(SiCl3)3 31 (Hauptprodukt), und es entstehen die Disilacyclobutane (Cl3Si)HC(SiCl2)2CH(SiCl3) 41 (cis, trans), (Cl3Si)2C(SiCl2)2CH(SiCl3) 45, das 1,3,5-Trisilacyclohexan [Cl3Si(H)C—SiCl2]3 44 sowie (Cl3Si)2CH—CH(SiCl3)2 und [(Cl3Si)2CH]2SiCl2. Aus (Cl3Si)2CClMe 39 bilden sich bevorzugt (Cl3Si)2C=CH2 und (Cl3Si)2CHMe neben HC(SiCl3)3, MeC(SiCl3)3 und (Cl3Si)3C—SiCl2Me. Aus Me2CCl2 59 entstehen bevorzugt Me(Cl)C=CH2, Me2CHCl sowie HCl2Si—CMe2—SiCl3 neben Me2C(SiCl3)2 und Me2C(SiCl2H)2. Verbindung 3 kristallisiert triklin in der Raumgruppe P1 (Nr. 2) mit a = 900,3, b = 914,0, c = 855,3 pm, α = 116,45°, β = 101,44°, γ = 95,86° und mit einem Molekül Pro Elementarzelle; 4: monoklin in der Raumgruppe C2/c (Nr. 15) mit a = 3 158,3, b = 1 103,7, c = 2 037,4 pm, β = 116,62° und mit 8 Molekülen pro Elementarzelle. In 3 ist der Disilacyclobutanring planar mit d(Si—C) = 191,8 pm und der üblichen Deformation in den endocyclischen Winkeln αSi = 94,2°〉 85,8° = αC. Im Bicyclus 4 sind die beiden spiroverknüpften Disilacyclobutanringe leicht gefaltet (19,0°) mit d(Si—C) = 190,4 pm am Spiro-C-Atom und d(Si—C) = 192,0 pm an den beiden anderen. Auch in 4 gilt für die endocyclischen Winkel αSi = 93,9° 〉 84,4° = αC.
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    Neue Komplexe des Titans mit silylierten Aminoiminophosphoran- und SulfodiimidligandenProfessor Heinrich Nöth zum 65. Geburtstage gewidmet (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1543-1550 
    Details
    ISSN: 0044-2313
    Keywords: Titanium Complexes ; Aminoiminophosphoranes ; Sulfodiimides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New Complexes of Titanium with Silylated Aminoiminophosphorane and Sulfodiimide LigandsTiCl4 forms a 1 : 1 adduct with S(NSiMe3)2 to give compound 1 and with Me2S(NSiMe3)2 compound 2, respectively. The reaction of TiCl4 with Ph2S(NSiMe3)2 yields the disubstituted compound Ph2S(NTiCl3)2X4THF 3 which crystallizes in space group P1. Reaction of TiCl4 with (Me3Si)2NPPh2NPPh2NSiMe3 leads to an exchange of one silyl group with a TiCl3 moiety. In this molecule the Ti-atom is only four-coordinated. The compound crystallizes in the space group P21/c. No chelate complexes are formed by reactions of CpTiCl3, Cp*TiCl3 and Cp*TiF3 with Ph2P(NSiMe3)2H, this is shown by X-ray structural analysis of Cp*TiCl2NPPh2NHSiMe3 6. Crystals of 6 are obtained in space group P1.
    Notes: TiCl4 bildet mit S(NSiMe3)2 und Me2S(NSiMe3)2 ein 1 : 1 Addukt (1, 2), während Ph2S(NSiMe3)2 die disubstituierte Verbindung Ph2S(NTiCl3)2X4 THF 3 ergibt, die in der Raumgruppe P1 kristallisiert. Setzt man TiCl4 mit (Me3Si)2NPPh2NPPh2NSiMe3 um, so wird die imidische Silylgruppe gegen eine TiCl3-Einheit ausgetauscht. Das Molekül, in dem das Ti-Atom nur vierfach koordiniert ist, bildet in der Raumgruppe P21/c Einkristalle. In den Komplexen von CpTiCl3, Cp*TiCl3 und Cp*TiF3 mit Ph2P(NSiMe3)2H erfolgt ebenfalls keine Chelatisierung wie die Einkristall-Röntgenstrukturanalyse von Cp*TiCl2NPPh2NHSiMe3 6 belegt. Verbindung 6 kristallisiert in der Raumgruppe P1.
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    Reaktionen des 1,1′, 3,3′-Tetrakis(dimethylamino)-1λ5, 3λ5-diphosphets mit S—H-aciden VerbindungenProfessor Rudolf Hoppe zum 70. Geburtstage gewidmet (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1551-1555 
    Details
    ISSN: 0044-2313
    Keywords: 1,′,3,3′-Tetrakis(dimethylamino)-1λ5, 3λ5-diphosphete ; sulfanolysis ; bis(dimethylamino)thiophos-phonylmethylidene-methyl-bis(dimethylamino)phosphorane ; 1,′, 3,3′ -tetrakis(dimethylamino)-2,4-bis-(ethylthio)-1λ5, 3λ5-diphosphete ; 1,′,3,3′-tetrakis(dimethyl-amino)-1,2-dihydro-3λ5-[1,3]-diphosphetiumthiophenolate ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of 1,′, 3,3′-Tetrakis(dimethylamino)-1λ5,3λ5-diphosphete with S—H Acidic Compounds.Reaction of 1,′,3,3′-tetrakis(dimethyl-amino)-1λ5,3λ5-diphosphete (1) with hydrogen sulfide yields bis(dimethylamino)thiophosphonylmethylidene-methyl-bis(dimethylamino)phosphorane (5).Water eliminates dimethylamine from 5 and forms bis(dimethyl-amino)thiophosphonyl-methyl(dimethylamino)phosphonylmethylene 6. The reaction of 1 with ethylmercaptane yields the 2,4-bis(ethylthio)-derivative of 1, i.e. compound 8 and bis(dimethylamino)phosphanylmethylidene-methyl-bis(dimethylamino)phosphorane (9), which is also formed from 1 and 2,4,6-trimethylphenylphosphane. Thiophenol protonates 1 to give the corresponding cation which is isolated as its thiophenolate, 10. Properties, nmr and mass spectra of 5, 6 and 8 - 10 are described and discussed.
    Notes: Die Reaktion von 1,′,3,3′-Tetrakis(dimethylamino)-1λ5, 3λ5 -diphosphet (1) mit Schwefelwasserstoff führt zu Bis(dimethylamino)thiophosphonylmethyliden-methyl-bis(dimethylamino)phosphoran(5). Wasser spaltet aus 5 Dimethylamin ab und bildet Bis(dimethylamino)thiophosphonyl-methyl(dimethylamino)phosphonylmethylen 6. Bei der Umsetzung von 1 mit Ethylmercaptan entstehen das 2,4-Bis(ethylthio)-Derivat von 1, die Verbindung 8 und Bis(dimethylamino)-phosphanylmethyliden-methyl-bis(dimethylamino)phosphoran (9), das auch aus 1 und 2, 4, 6-Trimethylphenyl-phosphan gebildet wird. Thiophenol protoniert 1 zum entsprechenden Kation, das als Thiophenolat 10 isoliert wird. Eigenschaften, NMR- und Massenspektren von 5, 6 und 8 - 10 werden beschrieben und diskutiert.
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    Zum Chemischen Transport von Cr2O3 mit Cl2 und mit HgCl2 — Experimente und ModellrechungenProfessor Heinrich Nöth zum 65. Geburtstage gewidmet (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1530-1542 
    Details
    ISSN: 0044-2313
    Keywords: Chromium oxide ; chemical vapour transport ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Chemical Transport of Cr2O3 with Cl2 and with HgCl2  -  Experiments and Model CalculationsThe migration of Cr2O3 in a temperature gradient (1 000°C → 900°C) in the presence of low concentrations of chlorine and water (from the wall of silica ampoules) is a result from the endothermic reactions (1) Cr2O3,s + H2Og + 3 Cl2,g = 2 CrO2Cl2,g + 2 HClg (2) Cr2O3,s + 1/2 O2,g + 2 Cl2,g = 2 CrO2Cl2,g With higher concentrations of chlorine, the transport reaction is (3) Cr2O3,s + 5/2 Cl2,g = 3/2 CrO2Cl2,g + 1/2 CrCl4,g The gas phase of the transport system Cr2O3/Cl2 can be reduced step by step by adding small amounts of chromium, so that CrCl3 and finally also CrCl2 become more important. Further, at a lower ratio n°(Cl)/n°(Cr) three transport reactions have to be taken into consideration; with the participation of CrOCl2,g (5).(4) Cr2O3,s + 9/2 CrCl4,g = 3/2 CrO2Cl2,g + 5 CrCl3,g (5) Cr2O3,s + 3 CrCl4,g = 3 CrOCl2,g + 2 CrCl3,g (6) Cr2O3,s + H2,g + 4 HClg = 2 CrCl2,g + 3 H2Og The reactions (1), (2) and (6) become possible through the cooperation of two transport agents at a time. The migration of Cr2O3 with HgCl2 can also be described with reactions (1) - (3). The decomposition of HgCl2 Produces the small chlorine pressure for the transport reaction. The oxidation potential of the transport agent HgCl2 is too low for the oxidation of CrIII to CrVI.
    Notes: Cr2O3 wandert bei Zugabe von Chlor im Temperaturgefälle von T2 = 1 000°C nach T1 = 900°C im Falle niedriger Transportmitteldichten und der Anwesenheit von H2O (aus der Ampullenwand) über die endothermen Transportgleichgewichte (1) Cr2O3,s + H2Og + 3 Cl2,g = 2 CrO2Cl2,g + 2 HClg (2) Cr2O3,s + 1/2 O2,g + 2 Cl2,g = 2 CrO2Cl2,g und bei höheren Transportmitteldichten über: (3) Cr2O3,s + 5/2 Cl2,g = 3/2 CrO2Cl2,g + 1/2 CrCl4,g Durch Zusatz von elementarem Cr zum Transportsystem Cr2O3/Cl2 läßt sich die Gasphase schrittweise reduzieren, sodaß CrCl3 und schließlich auch CrCl2 an Bedeutung gewinnt. Mit abnehmendem Verhältnis n°(Cl)/n°(Cr) sind drei weitere Transportgleichgewichte zu berücksichtigen; dabei tritt auch CrOCl2,g auf: (4) Cr2O3,s + 9/2 CrCl4,g = 3/2 CrO2Cl2,g + 5 CrCl3,g (5) Cr2O3,s + 3 CrCl4,g = 3 CrOCl2,g + 2 CrCl3,g (6) Cr2O3,s + H2,g + 4 HClg = 2 CrCl2,g + 3 H2Og Die Reaktionen Gl. (1), (2) und (6) werden durch das Zusammenwirken von jeweils zwei Transportmitteln („Transportmittelkombination“) ermöglicht. Der Transport von Cr2O3 mit HgCl2 ist ebenfalls auf Gl. (1) - (3) zurückzuführen; die in diesem Fall niedrigeren Cl2-Partialdrücke liefert der thermische Zerfall von HgCl2. Das Oxidationsvermögen des Transportmittels HgCl2 reicht nicht aus, um CrIII zu CrVI zu oxidieren.
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    K3Na26In48: An Intermetallic Phase with Large Pseudo-icosahedral Clusters and a Na46 Clathrate-I Network Enveloping a Covalent ∞3[In12] Cluster FrameworkDedicated to Professor Hartmut Bärnighausen on his 60th Birthday (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1556-1563 
    Details
    ISSN: 0044-2313
    Keywords: Indium Cluster Framework ; clathrate-I ; K3Na26In48 ; Synthesis ; Crystal Structure ; Properties ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: K3Na26In48: Eine intermetallische Phase mit großen pseudo-ikosaedrischen Clustern und einem Clathrat-I-Netz Na46, welches ein kovalentes Clusternetz ∞3[In12] einhülltK3Na26In48 bildet sich aus den Elementen in Form silberglänzender, spröder Kristalle in geschlossenen Niobampullen (aufgeschmolzen bei 873 K; getempert bei 573 K). Die Verbindung ist metallisch und sehr empfindlich gegen Luft und Feuchtigkeit. Die Kristallstruktur von K3Na26In48 (kubisch; Raumgruppe Pm3n, No. 223; a = 16,046(2) Å; Z = 2; Pearsonsymbol cP154) enthält Pro Elementarzelle zwei leere ikosaedrische In12ico-Cluster und sechs hexagonal-antiprismatische In12hap-Cluster mit einem Na-Atom im Zentrum. Sämtliche In12-Cluster sind durch je 12 kovalente Exo-Bindungen zu einem 3 D-Netz miteinander verbunden (In - In = 2,912 - 3,149 Å). Die übrigen Na-Atome bilden ein Na46-Netz vom Clathrat-I-Typ, dessen (2 + 6) Käfige die In12-Cluster einhüllen. Die neuartige Struktur kann als aufgefüllte Clathrat-I-Struktur angesehen werden: in der die [NaIn12hap]-Cluster durch K-Atome zu eindimensionalen Säulen verknüpft sind. Die K-Atome bilden auch ein (6,4)-Netz vom NbO-Typ mit Na-Atomen auf den Brückenpositionen. Die gesamte Struktur kann andererseits auch als kubisch-raumzentrierte Packung großer, mehrschaliger, kondensierter A122-Cluster von nahezu perfekter Ikosaedersymmetrie angesehen werden (Durchmesser 16 Å). Bindungsverhältnisse und strukturelle Zusammenhänge mit anderen Phasen werden eingehend diskutiert.
    Notes: K3Na26In48 was synthesized from the elements in sealed niobium ampoules (melted at 873 K; annealed at 573 K). The compound forms brittle crystals with silver metallic lustre, behaves as a metallic conductor, and is very sensitive to air and moisture. The crystal structure of K3Na26In48 (cubic; space group Pm3n,No. 223; a = 16.046(2) Å; Z = 2; Pearson symbol cP154) contains two empty icosahedral In12ico and six hexagonal antiprismatic In12hap indium clusters per unit cell. The latter are centered by Na atoms. All In12 clusters are interconnected by 12 exo-bonds forming a covalent 3 D network (In - In = 2.912 - 3.149 Å). The remaining Na atoms form a Na46 3 D-network of the clathrate-I type with (2 + 6) cages, enveloping the In12 clusters network. This novel structure can be regarded as a filled derivative of the clathrate-I structure: . The potassium atoms link the filled [NaIn12hap] clusters to 1 D columns, and also form (6,4) net of the NbO type with Na atoms at bridging positions. The whole structure can also be described as a bcc packing of huge condensed A122 clusters (16 Å diameter) which have nearly icosahedral symmetry and consist of several atomic shells. The bonding as well as the structural relationships to other phases are discussed in detail.
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    Clusteraufbau durch Photolyse von Azidokomplexen des Platins und Golds. Synthesen und Kristallstrukturen von [(Ph3PAu)6(AuCl)3Pt(CO)], [(dppe)PtCo2(CO)7] und [(Ph3PAu)4Pt(dppe)](PF6)2Professor Dietrich Mootz zum 60. Geburtstage gewidmet (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1564-1574 
    Details
    ISSN: 0044-2313
    Keywords: monoplatinum nonagold cluster cluster ; monoplatinum dicobalt cluster ; monoplatinum tetragold cluster ; [(Ph3PAu)6(AuCl)3Pt(CO)] ; [(dppe)PtCo2(CO)7] ; [(Ph3PAu)4Pt(dppe)](PF6)2 ; synthesis ; photolysis of azido complexes ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cluster Synthesis by Photolysis of Azido Complexes of Platinum and Gold. Syntheses and Crystal Structures of [(Ph3PAu)6(AuCl)3Pt(CO)], [(dppe)PtCo2(CO)7] and [(Ph3PAu)4Pt(dppe)](PF6)2Photolysis of a mixture of Ph3PAuN3, Ph3PAuCl and (Ph3P)2Pt(N3)2 in THF yields after chromatographic separation with CH2Cl2/EtOH as eluens the cluster [(Ph3PAu)6(AuCl)3Pt(CO)] (1). It crystallizes in the triclinic space group P1 with the lattice parameters a = 2 139.3(4), b = 2 457.1(4), c = 2 561.9(1) pm, α = 79.74(9)°, β = 80.06(6)°, γ = 66.05(5)°, Z = 4. The nine gold atoms form a fragment of an icosahedron with the platinum atom in its center. Upon photolysis of (dppe)Pt(N3)2 with Co2(CO)8 in THF one m̈2-CO ligand of the cobalt carbonyl is substituted by a (dppe)Pt group. The resulting cluster [(dppe)PtCo2(CO)7] (2) crystallizes monoclinically in the space group P21/n with a = 1 303.9(3), b = 1 768.1(8), c = 1 461.4(4) pm, β = 102.81(1)°, Z = 4. Photolysis of 2 with excess Ph3PAuN3 affords the clusters [(Ph3PAu)4Pt(dppe)]2+ (3), and [(Ph3PAu)6AuCo2(CO)6]+. 3 crystallizes with PF6- as counterions in the triclinic space group P1 with a = 1 369.1(4), b = 1 505.0(4), c = 2 773.0(8) pm, α = 84.74(1)°, β = 87.37(2)°, γ = 65.94(2)°, Z = 2. The Au4Pt skeleton of 3 forms a trigonal bipyramid with the platinum atom in equatorial position.
    Notes: Die Photolyse einer Mischung von Ph3PAuN3, Ph3PAuCl und (Ph3P)2Pt(N3)2 in THF ergibt nach chromatographischer Reinigung mit CH2Cl2/EtOH als Eluens den Cluster [(Ph3PAu)6(AuCl)3Pt(CO)] (1). Er kristallisiert triklin in der Raumgruppe P1 mit den Gitterkonstanten: a = 2 139,3(4), b = 2 457,1(4), c = 2 561,9(1) pm, α = 79,74(9)°, β = 80,06(6)°, γ = 66,05(5)°, Z = 4. Die neun Goldatome bilden ein Ikosaederfragment, in dessen Zentrum sich das Pt-Atom befindet. Bei der Photolyse einer Mischung von (dppe)Pt(N3)2 mit Co2(CO)8 in THF wird ein m̈2-CO-Ligand des Cobaltcarbonyls durch eine (dppe)Pt-Gruppe substituiert. Der resultierende Cluster [(dppe)PtCo2(CO)7] (2) kristallisiert monoklin mit der Raumgruppe P21/n und a = 1 303,9(3), b = 1 768,1(8), c = 1 461,4(4) pm, β = 102,81(1)°, Z = 4. Die Photolyse von 2 mit überschüssigem Ph3PAuN3 führt auf die Cluster [(Ph3PAu)4Pt(dppe)]2+ (3) und [(Ph3PAu)6AuCo2(CO)6]+. 3 kristallisiert als PF6- -Salz in der triklinen Raumgruppe P1 mit a = 1 369,1(4), b = 1 505,0(4), c = 2 773,0(8) pm, α = 84,74(1)°, β = 87,37(2)°, γ = 65,94(2)°, Z = 2. Das Au4Pt-Gerüst von 3 bildet eine trigonale Bipyramide mit dem Pt-Atom in äquatorialer Position.
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    Über Tris[(trialkylphosphan)gold(I)]oxonium-tetrafluoroborate und Tris[(triphenylphosphan)gold(I)]sulfonium-tetrafluoroborat (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1575-1579 
    Details
    ISSN: 0044-2313
    Keywords: Tris[(trialkylphosphine)gold(I)]oxonium salts ; tris[(triphenylphosphine)gold(I)]sulfonium salts ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Tris[(trialkylphosphine)gold(I)]oxonium Tetrafluoroborates and Tris[(triphenylphosphine)gold(I)]sulfonium Tetrafluoroborate[Et3PAu]+BF4-, obtained from Et3PAuCl and AgBF4 in tetrahydrofuran, reacts with KOH (molar ratio 3:1) to give the oxonium salt [(Et3P)Au]3O+BF4- (1). The homologous [t(Bu3P)Au]3O+BF4- (2) is generated similarly from tBu3PAuCl and Ag2O in the presence of NaBF4 in THF. The composition and identity of these two first tris[(trialkylphosphine)gold(I)]oxonium salts have been confirmed by analytical and spectroscopic data. The compounds are useful aurating agents. From the corresponding triphenylphosphine complex and (Me3Si)2S quantitative yields of the sulfonium salt [(Ph3P)Au]3S+BF4- (3) are obtained. Its crystal structure features monomeric cations, and in these small Au—S—Au angles indicate significant metal-metal bonding.
    Notes: Das durch Umsetzung von Et3PAuCl mit AgBF4 entstehende [Et3PAu]+BF4- ergibt mit KOH (Molverhältnis 3:1) in Tetrahydrofuran das Oxonium-Salz [(Et3P)Au]3O+BF4- (1). Ähnlich entsteht aus Bu3PAuCl und Ag2O in Gegenwart von NaBF4 in THF das homologe [(tBu3P)Au]3O+BF4- (2). Diese beiden ersten Tris[(trialkylphosphan)gold(I)]oxonium-Salze wurden durch analytische und spektroskopische Daten in ihrer Zusammensetzung und Identität gesichert. Sie sind wichtige Aurierungsreagentien. Aus dem zugehörigen Triphenylphosphan-Komplex entsteht mit (Me3Si)2S quantitativ das Sulfonium-Salz [(Ph3P)Au]3S+BF4- (3). Seine Kristallstrukturanalyse zeigt monomere Trigoldsulfonium-Kationen mit steiler SAu3-Pyramide. Kurze Au … Au-Abstände und kleine Au—S—Au-Winkel deuten signifikante Au  -  Au-Wechselwirkungen an.
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  • 139
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    Ba3V2O4F8: [V4(O,F)20]8- tetrameric groups of octahedra inserted a tridimensional network of (FBa4) tetrahedra (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1597-1602 
    Details
    ISSN: 0044-2313
    Keywords: Barium vanadium oxide fluorides ; crystal structures ; bond valence calculations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ba3V2O4F8: [V4(O,F)20]8- tetramere Gruppen von Oktaedern in einem dreidimensionalen Netz von (FBa4)-TetraedernBa3V2O4F8 wird durch hydrothermale synthese dargestellt und die Kristallstruktur aus Einkristalldaten bestimmt: Raumgruppe: Pnnm, Z = 4, a = 9,945(4), b = 10,277(1), c = 9,673(1) Å; R = 0,0331, Rw = 0,0315 für 892 unabhängige Reflexe und 86 freie Parameter. Die Struktur ist verwandt mit der von Ba3Al2F12 und kann durch isolierte, tetramere [V4(O,F)20]8--Gruppen von Oktaedern in einem dreidimensionalen Netz von (FBa4)-Tetraedern beschrieben werden. Die Anordnung der Sauerstoff- und Fluoratome wird mit Hilfe von Valenzband-Rechnungen diskutiert.
    Notes: Ba3V2O4F8 is prepared by hydrothermal synthesis. The crystal structure is established from single crystal X-ray diffraction data: Space group Pnnm, Z = 4, a = 9.945(4) Å, b = 10.277(1) Å and c = 9.673(1) Å R = 0.0331, Rw = 0.0315 for 892 independent reflections and 86 parameters. The structure is related to that Ba3Al2F12 and is described in terms of isolated [V4(O,F)20]8- tetrameric groups of octahedra inserted in a tridimensional network of (FBa4) tetrahedra. Location of oxygen and fluorine atoms is discussed with the help of bond valence calculations.
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    Sulfur Compounds. 164 Thermal Polymerization of the Cyclic Seleniumsulfide 1,2-Se2S5 Studied by DSC, HPLC, Raman Spectroscopy, and X-Ray Diffraction (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1589-1596 
    Details
    ISSN: 0044-2313
    Keywords: Seleniumsulfides ; thermal polymerization ; DSC ; HPLC ; Raman spectroscopy ; X-ray diffraction ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Schwefelverbindungen. 164. Thermische Polymerisation des cyclischen Selensulfids 1,2-Se2S5 - eine Untersuchung mittels DSC, HPLC, Ramanspektroskopie und RöntgenbeugungKristallines 1,2-Se2S5 polymerisiert bei 47°C endotherm zu einem kettenförmigen Polymer, das nach Streckung und Extraktion aus helicalen Molekülen ähnlich denen im polymeren Schwefel besteht. Beim Erhitzen zersetzt sich das Polymer bei 84°C exotherm zu einer Mischung aus sieben cyclischen SenS8-n-Molekülen; diese Mischung schmilzt bei 111°C. Wenn das polymere Se2S5 mit CS2 gekocht wird, enstehen primär 1,2-Se2S5, SeS5 und 1,2,3-Se3S5, aber zusätzlich werden SeS7 und 1,2-Se2S6 beobachtet.Diese Ergebnisse sprechen für die Atomfolge -Se—S5—Se- in dem Polymer, dessen Pulverdiagramm, Gitterkonstanten und Ramanspektrum mitgeteilt werden.
    Notes: Solid 1,2-Se2S5 polymerizes endothermically at 47°C to give a linear polymer which after stretching and extraction consists of helical molecules similar to those of polymeric sulfur. Heating of the polymer results in slow exothermic depolymerization at 84°C to give a mixture of seven cyclic SenS8-n molecules which melts at 111°C. When the polymeric Se2S5 is refluxed with CS2 the initial depolymerization Products are 1,2-Se2S5, SeS5 and 1,2,3-Se3S5 but in addition SeS7 and 1,2-Se2S6 are formed. These results indicate the atomic sequence -Se—S5—Se- in the polymer. The powder x-ray diffraction pattern and Raman spectrum of the polymer as well as its lattice parameters are reported and the Probable mechanism of its depolymerization is discussed.
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    Some Tris[(triorganophosphine)gold(I)]-oxonium and -Organoimonium Tetrafluoroborates with Bulky Substituents (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1580-1588 
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    ISSN: 0044-2313
    Keywords: Gold(I) Complexes ; (Triorganophosphine)gold(I) Complexes ; Tris[(triorganophosphine)gold(I)]oxonium Salts ; Tris[(triorganophosphine)gold(I)]imonium Salts ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Tris[(triorganophosphan)gold(I)]oxonium- und -organoimoniumtetrafluoroborate mit voluminösen SubstituentenTris{[tri(2-methylphenyl)phosphan]gold(I)}-, Tris{[tri(2,4,6-trimethylphenyl)phosphan]gold(I)}- und Tris{[tri(cyclohexyl)phosphan]gold(I)}-oxonium-tetra-fluoroborat (1-3) wurden aus den entsprechenden (Phosphan)gold(I)-chloriden, Silberoxid und Natrium-tetrafluoroborat in Aceton hergestellt. Diese Oxonium-Salze sind ausgezeichnete Aurierungsreagenzien. So entstehen aus 1 und t-Butylamin tBuNH2 oder Anilin PhNH2 in guten Ausbeuten die dreikernigen Imino-Komplexe {[(2-MeC6H4)3P]Au}3NtBu+BF4- (4) bzw. {[(2-MeC6H4)3P]Au}3NPh+BF4- (5). Mit 3 ergeben sowohl Anilin als auch 8-Amino-chinolin die Produkte {[(c-C6H11)3P]Au}3NPh+BF4- (6) bzw. {[(c-C6H11)3P]Au}3N(C9H6N)+BF4- (7. Die Aurierung von Anilin mit dem sterisch am meisten gehinderten Reagens 2 ergibt nur den zweikernigen Komplex {[(2,4,6-Me3C6H2)3P]Au}2N(Ph)H+BF4- (8). Die Reagenzien 1-3 und die Produkte 4-8 wurden durch analytische und NMR-spektroskopische Daten charakterisiert, und die Kristallstrukturen von 4 und 6 wurden durch Einkristall-Röntgenbeugung bestimmt. In den Kationen von 4 findet man ein Dreieck aus Goldatomen [mit kurzen Au  -  Au-Kontakten von 3,036(1), 3,107(1) und 3,214(1) Å], die mit dem Stickstoffatom eine steile Pyramide bilden, deren Au—N—Au-Winkel viel kleiner sind als der Tetraeder-Richtwert von 109,7°, nämlich 94,8(4), 98,1(4) und 103,0(4)°. Die Au3-Gruppe steht relativ zu den Methylgruppen der t-Butyl-Gruppe auf Lücke. Für 6 sind die Resultate ähnlich [Au…Au: 3,037(1), 3,071(1), 3,222(1) Å; Au—N—Au: 95,3(3), 96,5(3), 103,6(3)°]. NMR-Spektren bei variabler Temperatur zeigen für die Verbindungen 3 und 8 eine gehinderte Rotation der Mesityl-Gruppen um die P—C-Bindungen der Liganden, die auf die räumliche Überladung zurückgeht.
    Notes: Tris{[tri(2-methylphenyl)phosphine]gold(I)}-, tris{[tri(2,4,6-trimethylphenyl)phosphine]gold(I)}- and tris{[tri(cyclohexyl)phosphine]gold(I)}-oxonium tetra-fluoroborate (1-3) have been prepared from the corresponding (phosphine)gold(I) chlorides, silver oxide, and sodium tetrafluoroborate in acetone. These oxonium salts are excellent aurating agents for primary amines. Thus in the reaction with 1, t-butylamine tBuNH2 and aniline PhNH2 are readily converted into the trinuclear imino complexes {[(2-MeC6H4)3P]Au}3NtBu+BF4- (4) and {[(2-MeC6H4)3P]Au}3NPh+BF4- (5) in high yields. With 3, both aniline and 8-amino-quinoline also give the trinuclear complexes, i.e. {[(c-C6H11)3P]Au}3 NPh+BF4- (6) and {[(c-C6H11)3P]Au}3N(C9H6N)+BF4- (7). Auration of aniline with the most sterically hindered reagent 2 yields only the binuclear complex {[2,4,6-Me3C6H2)3P] · Au}2N(Ph)H+BF4- (8). The reagents 1-3 and the Products 4-8 have been characterized by analytical and NMR spectroscopic data, and the crystal structures of compounds 4 and 6 have been determined by single crystal x-ray diffraction. In the cations of 4, a triangle of gold atoms with short Au  -  Au contacts [3.036(1), 3.107(1), and 3.214(1) Å] forms a steep pyramid with the nitrogen atom, in which the angles Au—N—Au are all much smaller than the tetrahedral standard of 109.7°: 94.8(4), 98.1(4), and 103.0(4)°. This triangular Au3 unit is staggered relative to the three methyl groups of the tBu substituent at nitrogen. The results for 6 are similar [Au  -  Au: 3.037(1), 3.071(1), and 3.222(1) Å; Au—N—Au: 95.3(3), 96.5(3), and 103.6(3)°]. Variable temperature NMR studies of compounds 3 and 8 show hindered rotation of the mesityl groups about the P—C bonds of the ligands originating from the steric congestion within each tertiary phosphine.
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    Über die Synthese von Tris(trimethylsilyl)silyl-kalium, -rubidium und -caesium und die Molekülstrukturen zweier Toluolsolvate (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1777-1789 
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    ISSN: 0044-2313
    Keywords: Metal Silyls ; Tris(trimethylsilyl)silyl Potassium ; Tris(trimethylsilyl)silyl Rubidium ; Tris(trimethylsilyl)silyl Cesium ; Alkali Metal Toluene Adducts ; X-ray Structures ; Spectroscopic Data ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: About the Synthesis of Tris(trimethylsilyl)silyl Potassium, Rubidium and Cesium and the Molecular Structures of two Toluene Solvates.Solventfree tris(trimethylsilyl)silyl potassium (1), rubidium (2) and cesium (3) are obtained by the reaction of the zink group bis[tris(trimethylsilyl)silyl] derivatives with the appropriate alkali metal in n-pentane. Addition of benzene or toluene to the colourless powders yields deeply coloured solutions. From these solutions single crystals of tris(trimethylsilyl)silyl rubidium - toluene (2/1) (2 a) and tris(trimethylsilyl)silyl cesium - toluene (2/3) (3 a) suitable for X-ray structure analysis are iso- lated [2a: orthorhombic; P212121; a = 1 382.1(3); b = 1 491.7(5); c = 2 106.3(6) pm; Z = 4 (dimers); 3a: orthorhombic; P212121; a = 2 131.0(6); b = 2 833.1(2); c = 925.2(2) pm; Z = 4 (dimers)]. The central structure moieties are folded four-membered Rb2Si2 and Cs2Si2 rings, respectively. Small Si—Si—Si angles (100 to 104°) on the one hand and extreme highfield 29Si-NMR shifts of the central silicon atoms on the other hand indicate a strong charge transfer from the alkali metal atoms to the tris(trimethylsilyl)silyl fragments, i.e. mainly ionic interactions between alkalimetal and silicon atoms.
    Notes: Die Umsetzung der Bis[tris(trimethylsilyl)silyl]-Derivate der Zink-Gruppe mit Kalium, Rubidium und Caesium in n-Pentan liefert Tris(trimethylsilyl)silyl-kalium (1), -rubidium (2) und -caesium (3) als farblose, pyrophore Pulver. Nach Zugabe von Benzol order Toluol zu den solvensfreien Verbindungen bilden sich lösliche, farbige Aromaten-Solvate. An den Addukten Tris(trimethylsilyl)silyl-rubidium - Toluol (2/1) (2 a) und Tris(trimethylsilyl)silyl-caesium - Toluol (2/3) (3 a) wurden Kristallstrukturanalysen durchgeführt [2a: orthorhombisch; P212121; a = 1 382,1(3); b = 1 491,7(5); c = 2 106,3(6) pm; Z = 4 (Dimere); 3a: orthorhombisch; P212121; a = 2 131,0(6); b = 2 833,1(2); c = 925,2(2) pm; Z = 4 (Dimere)]. Demzufolge liegen sie im Festkörper als dimere Moleküle mit viergliedrigen, gefalteten Rb2Si2-bzw. Cs2Si2-Ringen vor. Die mit 100 bis 104° relativ kleinen Si—Si—Si-Winkel deuten ebenso wie die im 29Si-NMR-Spektrum beobachtete extreme Tieffeldverschiebung der Resonanzen des zentralen Siliciumatoms auf eine weitgehende Ladungsübertragung von den Alkalimetallatomen auf das Tris(trimethylsilyl)silyl-Fragment, d. h. vorwiegend ionische Wechselwirkungen in den Ringen aus Alkalimetall- und Siliciumatomen hin.
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    Reaktivität von Monophosphan-Platin(0)-Verbindungen gegenüber Schwefeldioxid (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1793-1800 
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    ISSN: 0044-2313
    Keywords: Monophosphine Platin(0) Complexes ; SO2 Ligand ; Vinylsilyl Ligands ; Pt3 Cluster ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactivity of Monophosphine Platinum(0) Complexes with SO2.The addition reaction of (PPh3)Pt(ViSi) (ViSi = {η2-H2C=CHSiMe2}2O) (1) with SO2 gives within 30 min the red SO2 complex (PPh3)Pt(η2-H2C=CHSiMe2- OSiMe2CH=CH2)(SO2) (2). A reaction time of 24 h with SO2 leads to the elimination of the ViSi ligand, and the unstable monomeric intermediate (PPh3)Pt(SO2) cyclo- trimerizes to the stable cluster [Pt(PPh3)(SO2)]3 (3). 3 is also obtained within 30 min by the reaction of (PPh3)Pt(C2H4)2 (4) with SO2. The crystal structure of 3 has been determined; space group P21/n, Z = 4, a = 1 606.1(3), b = 1 019.3(1), c = 3 624.6(5) pm, β = 93.67°, R/Rw = 0.102/0.121.
    Notes: Die Reaktion von (PPh3)Pt(ViSi) (ViSi = {η2-H2C=CHSiMe2}2O) (1) mit SO2 führt nach 30 min unter Addition zum roten SO2-Komplex (PPh3)Pt(η2-H2C=CHSiMe2OSiMe2CH=CH2)(SO2) (2). Bei längerer Reaktionszeit (24 h) wird der ViSi-Ligand vollständig abgespalten und das instabile monomere Intermediat (PPh3)Pt(SO2) cyclotrimerisiert zum stabilen Cluster [Pt(PPh3)(SO2)]3 (3). Verwendet man (PPh3)Pt(C2H4)2 (4) als Edukt, entsteht 3 unter SO2-Atmosphäre innerhalb einer halben Stunde. 3 kristallisiert in der Raumgruppe P21/n, Z = 4, a = 1 606,1(3), b = 1 019,3(1), c = 3 624,6(5) pm, β = 93,67°, R/Rw = 0,102/0,121.
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    Alkalimolybdotellurate: Darstellung und Kristallstruktur von Rb6[TeMo6O24] · 10H2O und Rb6[TeMo6O24] · Te(OH)6 · 6H2O (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1834-1840 
    Details
    ISSN: 0044-2313
    Keywords: Rubidium hexamolydotellurates ; telluric acid ; X-ray structure analysis ; hydrogen bonding ; differential thermal analysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Alkaline Molybdotellurates: Preparation and Crystal Structures of Rb6[TeMo6O24] · 10H2O and Rb6[TeMo6O24] · Te(OH)6 · 6H2OSingle crystals of Rb6[TeMo6O24] · 10 H2O and Rb6[TeMo6O24] · Te(OH)6 · 6 H2O, respectively, were grown from aqueous solution. Rb6[TeMo6O24] · 10 H2O possesses the space group P1. The lattice dimensions are a = 963.40(13), b = 972.56(12), c = 1 056.18(13) pm, α = 97.556(10), β = 113.445(9), γ = 102.075(10)°; Z = 1, 2 860 reflections, 215 parameters refined, Rg = 0.0257. The centrosymmetrical [TeMo6O24]6- anions are stacked parallel to [010]. Rb(2) is coordinated with one exception by water molecules only. Folded chains consisting of [TeMo6O24]6- anions and Rb(2) coordination polyhedra which are linked to pairs represent the prominent structural feature.Rb6[TeMo6O24] · Te(OH)6 · 6 H2O crystallizes monoclinically in the space group C2/c with a = 1 886.4(3), b = 1 000.9(1), c = 2 126.5(3) pm, and β = 115.90(1)°; Z = 4, 3 206 reflections, 240 parameters refined, Rg = 0.0333. It is isostructural in high extent with (NH4)6[TeMo6O24] · Te(OH)6 · 7 H2O. Hydrogen bonds between Te(OH)6 molecules and [TeMo6O24]6- anions establish infinite strands. The [TeMo6O24]6- anions gather around Te(OH)6 providing channel-like voids extending parallel to [001].
    Notes: Einkristalle von Rb6[TeMo6O24] · 10 H2O und von Rb6[TeMo6O24] · Te(OH)6 · 6 H2O wurden in wässeriger Lösung gezüchtet. Rb6[TeMo6O24] · 10 H2O kristallisiert in der triklinen Raumgruppe P1 mit a = 963,40(13), b = 972,56(12), c = 1 056,18(13) pm, α = 97,556(10), β = 113,445(9), γ = 102,075(10)°, Z = 1; 2 860 Reflexe, 215 verfeinerte Parameter, Rg = 0,0257. Die zentrosymmetrischen [TeMo6O24]6--Anionen sind parallel zueinander entlang [010] gestapelt. In der Koordinationssphäre des Rb(2) treten mit einer Ausnahme lediglich Kristallwassermoleküle auf (KZ 8). Es liegen stark gewinkelte Ketten aus [TeMo6O24]6--Anionen und paarweise verknüpften Rb(2)-Koordinationspolyedern vor.Rb6[TeMo6O24] · Te(OH)6 · 6 H2O kristallisiert monoklin in der Raumgruppe C2/c mit a = 1 886,4(3), b = 1 000,9(1), c = 2 126,5(3) pm, β = 115,90(1)°; Z = 4, 3 206 Reflexe, 240 verfeinerte Parameter, Rg = 0,0333. Es ist weitgehend isostrukturell mit (NH4)6[TeMo6O24] · Te(OH)6 · 7 H2O. Unendliche Stränge aus zentrosymmetrischen Te(OH)6-Molekülen, die mit ebenfalls zentrosymmetrischen [TeMo6O24]6--Anionen durch Wasserstoffbrücken-bindungen verbunden sind, stellen das charakteristische Strukturmerkmal dar. Von den [TeMo6O24]6--Anionen werden die Te(OH)6-Moleküle kanalartig umschlossen.
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    Pb3Fe2F12: A new fluorometallate with a tetrameric structural unit (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1850-1856 
    Details
    ISSN: 0044-2313
    Keywords: Fluorometallate ; Lead Iron Fluoride ; Crystal Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pb3Fe2F12: ein neues Fluorometallat mit einer tetrameren BaueinheitPb3Fe2F12 wurde durch Hydrothermal-Synthese hergestellt und kristallisiert triklin in P1 mit a = 7,403(2) Å, b = 7,621(2) Å, c = 9,890(3) Å, α = 110,45(2)°, β = 107,98(1)°, γ = 95,92(2)°, V = 483,12(4) Å3, Z = 2. Zur Strukturbestimmung wurden von einem Einkristall 3 913 symmetrie-unabhängige gemessene Reflexe gesammelt (R = 0,045 und Rw = 0,045). Die Struktur ist durch das Vorliegen tetramerer isolierter Baugruppen [Fe4F20]8- charakterisiert. Ihre Ringform entspricht der von [Al4F20]8- in Ba3Al2F12. „Isolierte“ F- werden beobachtet und ihre Kationenkoordinationen diskutiert. Im Gegensatz zu Ba3Al2F12 sind hier alle Ringe einander parallel angeordnet.
    Notes: Pb3Fe2F12 grown by hydrothermal synthesis, crystallizes in the triclinic system, space group P1, with a = 7.403(2) Å, b = 7.621(2) Å, c = 9.890(3) Å, α = 110.45(2)°, β = 107.98(1)°, γ = 95.92(2)°, V = 483.12(4) Å3, Z = 2. The structure was solved from single crystal data using 3 913 independent reflections (R = 0.045 and Rw = 0.045). Characteristical of this structure is the presence of isolated tetrameric groups [Fe4F20]8- in form of “rings” as previously observed in Ba3Al2F12. “Independent” fluorine ions are also located and their cationic coordination is discussed. In contrast to Ba3Fe2F12, all the rings are parallel in the structure.
    Additional Material: 8 Ill.
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    A series of Mixed-Valent Molybdenum Monophosphates, isotypic with leucophosphite represented by CsMo2P2O10 and K1.5Mo2P2O10 · H2O (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1841-1849 
    Details
    ISSN: 0044-2313
    Keywords: Mixed valent Molybdenum(IV/V) and (III/IV/V)phosphates ; single crystal structure ; Leucophosphite frameworks ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Eine Reihe von gemischt-valenten Molybdänmonophosphaten - isotyp mit Leucophosphiten wie CsMo2P2O10 und K1,5Mo2P2O10 · H2ODie Struktur von zwei gemischtvalenten Molybdänphosphaten, CsMo2P2O10 und K1,5Mo2P2O10 · H2O, wurde mittels Einkristall-Röntgen-Strukturanalyse bestimmt: Raumgruppe P21/c mit a = 9,428(1), b = 9,943(2), c = 12,348(2) Å, β = 127,38(1)° für CsMo2P2O10 und a = 9,721(2), b = 9,805(3), c = 12,329(3) Å, β = 128,73(2)° für K1,5Mo2P2O10 · H2O. Diese Verbindungen sind isotyp mit NH4Mo2P2O10 · H2O und RbMo2P2O10 · (1 - x)H2O, die die Leucophosphitstruktur repräsentieren. Die Möglichkeit eines Kationdefizits in dieser Struktur wird durch die Synthese der zwei isotypen Verbindungen A1,5Mo2P2O10 · xH2O (A = Rb, Tl) gezeigt. In diesen Monophosphaten ist eine Lage Mo(1) voll besetzt mit MoV, während die andere oktaedrische Lage Mo(2) mit Molybdän unterschiedlicher Valenz MoIII, MoIV bis MoV besetzt wird. Der wesentlichste Unterschied zwischen diesen verschiedenen Phosphaten beruht auf der Verteilung der A-Kationen in den Tunneln in Abhängigkeit von ihrer Größe und Art.
    Notes: The structure of two mixed valent molybdenum phosphates, CsMo2P2O10 and K1.5Mo2P2O10 · H2O has been solved from single crystals by X-ray diffraction in the space group P21/c with a = 9.428(1), b = 9.943(2), c = 12.348(2) Å and β = 127.38(1)° for CsMo2P2O10 and a = 9.721(2), b = 9.805(3), c = 12.329(3) Å and β = 128.73(2)° for K1.5Mo2P2O10 · H2O. These compounds isotypic with NH4Mo2P2O10 · H2O and RbMo2P2O10 · (1 - x)H2O exhibit the leucophosphite structure. The possibility of cationic non stoichiometry in this structure is also shown by the synthesis of two isotypic compounds A1.5Mo2P2O10 · xH2O (A = Rb, Tl). In these monophosphates, one site Mo(1) is fully occupied by MoV, whereas the other octahedral site Mo(2) exhibits a variable valency MoIII—MoIV to MoV. The main difference between these different phosphates deals with the distribution of the A cations inside the tunnels, depending upon their size and their content.
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    Cyclodisilazane Synthese, Substitution und Kopplung (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1857-1861 
    Details
    ISSN: 0044-2313
    Keywords: 1-Amino-3-fluoro-1,3-disilazanes ; non symmetrically substituted cyclodisilazane ; ring cleavage ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cyclodisilazanes Synthesis, Substitution, Coupling1-Amino-3-fluoro-1,3-disilazanes react with n-butyllithium to give cyclodisilazanes. Metallization of the rings allows a stepwise substitution with silylgroups and ring coupling via silylgroups. Compound 14 is as well an endo- as exocyclic non symmetrically substituted cyclodisilazane. Ring cleavage occurs in the reaction of compound 4 with H2O (17) or NH3 (18).
    Notes: 1-Amino-3-fluor-1,3-disilazane reagieren mit n-BuLi zu Cyclodisilazanen. Die Metallierung der Ringe ermöglicht die schrittweise Mono- bzw. Disubstitution mit Silylgruppen und eine Kopplung über Silylgruppen. Ein sowohl endo- als auch exocyclisch unsymmetrisch substituiertes Cyclodisilazan wurde isoliert. Durch Ammonolyse und Hydrolyse entstehen unter Si—N-Ringspaltung ein 1,3-Bis(amino)- bzw. ein 1-Amino-3-hydroxy-1,3-disilazan.
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    Molecular and crystal structure of Bis(η5-cyclopentadienyl)titanium(IV) Dibromide, Ti(η5-C5H5)2Br2 (1993)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 619 (1993), S. 1927-1930 
    Details
    ISSN: 0044-2313
    Keywords: Metallocene dihalides ; titanocene dibromide ; X-ray analysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Molekular- und Kristallstruktur von Bis(η5-cyclopentadienyl)titan(IV)-dibromidDie Molecular- und Kristallstruktur von Bis(η5-cyclopentadienyl)titan(IV)-dibromid wurde durch Röntgenstrukturanalyse bestimmt. Kristalldaten: Triklin, Raumgruppe P1, a = 7,872(5), b = 11,807(5), c = 12,310(3) Å, α = 107,62(3), β = 100,83(4), γ = 90,69(4)°, V = 1 068(14) Å3, T = 293, Z = 4 (mit zwei kristallographisch unabhängigen Molekülen in der Elementarzelle und ähnlicher Konformation). Abschließende R-Werte: R = 0,068 und Rw = 0,073. Die Strukturergebnisse werden mit denen analoger Verbindungen verglichen.
    Notes: The crystal and molecular structure of Bis(η5-cyclopentadienyl)titanium(IV) dibromide, Ti(η5-C5H5)2Br2, has been investigated by an X-ray structure determination. Crystal data: triclinic, a = 7.872(5), b = 11.807(5), c = 12.310(3) Å, α = 107.62(3), β = 100.83(4), γ = 90.69(4)°, V = 1 068(14) Å3, T = 293, space group P1, Z = 4 (there are two crystallographically independent molecules in the asymmetric unit cell and their conformations are similar). Final R and Rw values are 0.068 and 0.073, respectively. The structural results are compared to those for similar type molecules.
    Additional Material: 2 Ill.
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    Reaktive E = C(p-p)π-Systeme, XXXIII. Side-on-Koordination des Phosphaalkins P ≡ C  -  N(iPr)2 im 16e-Nickel(0)-Komplex Ni(CO)PCy3[PCN(iPr)2] (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 63-65 
    Details
    ISSN: 0009-2940
    Keywords: Phosphaalkyne, amino- ; Nickel carbonyl phosphane complex ; π Coordination ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactive E = C(p-p)π Systems, XXXIII.  -  Side-on Coordination of the Phosphaalkyne P ≡ C  -  N(iPr)2 in the 16e Nickel(0) Complex Ni(CO)PCy3[PCN(iPr)2]The reaction of (diisopropylamino)phosphaethyne P ≡ C  -  N(iPr)2 with the nickel complex [Ni(CO)3PCy3] - in contrast to the analogous reactions with Ni(CO)4 or Ni(CO)3PR3 (R = Me, Ph) - leads to the novel 16e nickel(0) system [Ni{η2-P ≡ C  -  N(iPr2)}(CO)PCy3] with a planar geometry of all skeleton atoms besides the methyl and cyclohexyl groups. Side-on coordination of the P ≡ C triple bond results in an increase of the PC distance to 1.665 Ȧ typical for phosphaalkenes.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19931260111
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  • 150
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    1-Alkynyl Disulfides: Their Characterization and Their 1-Thiapropargyl  -  3-Thiaallenyl Rearrangements (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 73-77 
    Details
    ISSN: 0009-2940
    Keywords: 1-Alkynyl disulfides ; Thioketenes, thio-substituted ; α-Dithiones ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of novel 1-alkynyl disulfides 1 is described together with their 1-thiapropargyl  -  3-thiaallenyl rearrangement and a [1,3]-sigmatropic shift of 1-alkynyl amino disulfides, followed by rearrangement of the aminothio-substituted thioketenes so formed.
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    Medium-Sized Cyclophanes, 25. Bromination of [2.n]Metacyclophan-1-enes and Isolation of Two Isomers of 1-Bromo[2.n]metacyclophan-1-enes (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 447-451 
    Details
    ISSN: 0009-2940
    Keywords: Dimethyl[2.n]metacyclophan-1-ene ; Bromination ; cis Addition ; Dehydrobromination ; (E) and (Z) isomers ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bromination of dimethyl[2.3]metacyclophan-1-ene (1b) with bromine affords the cis adduct 6b resulting from the addition to the bridging double bond; a similar reaction of dimethyl[2.4]metacyclophan-1-ene (1c) gives a mixture of the cis and trans adduct formed by the addition to the bridged double bond along with the products containing a brominated internal methyl group. On the other hand, bromination of dimethy1[2.n]metacyclophan-1-enes (1) with benzyltrimethylammonium tribromide affords exclusively the product of the cis addition 6 to the bridged double bond. Treatment of [3.2]metacyclophane 6b with potassium tert1-butoxide in refluxing tBuOH for 1 h gives the dehydrobrominated product (E)-8b in 95% yield; a similar reaction of [4.2]metacyclophane 6c furnishes two isomers, (E)-8c and (Z)-8c, of 1-bromo[2.4]1-metacyclophan-1-ene along with [2.4]metacyclophan-1-one 9c in 20% yield. The characterization and the reaction pathway of these products are discussed.
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    Übergangsmetallaktivierte organische Verbindungen, XXXVII. über eine neue Aldehyd-und Ketonreaktion: Synthese und spektroskopische Untersuchung von α1-Phosphonioalkoxy-übergangsmetallkomplexenHerrn Professor Ulrich Schöllkopf zum 65. Geburtstag gewidmet. (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 453-457 
    Details
    ISSN: 0009-2940
    Keywords: Aldehydes ; Ketones ; Titanium complexes ; Niobium complexes ; Tantalum complexes ; Phosphonium chlorides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transition Metal-Activated Organic Compounds, XXXVII[1].  -  A Novel Reaction of Aldehydes and Ketones: Synthesis and Spectroscopic Investigation of α1-Phosphonioalkoxy Transition Metal ComplexesHerrn Professor Ulrich Schöllkopf zum 65. Geburtstag gewidmet.By treatment of aldehydes and ketones with one mole equivalent of a Lewis acid (TiCl4, NbCl5, TaCl5) and one mole equivalent of PPh3, or in one case of Ph2PCH2CH2PPh2, the aldehyde derivates [R1CH(P+Ph2R2)-OMCln]Cl- (4-8; M=Ti, Nb, Ta; R2=Ph or CH2CH2PPh2) and the ketone derivatives [R1R2C(P+Ph3)-ONbCl4]Cl- (9-10) were prepared. Complexes 4-10 were isolated as air-and water-sensitive solids. According to the NMR spectra some of the obtained aldehyde derivatives 4-8 exist in solution as a mixture of isomers or oligomers, whereas the ketone derivatives 9 and 10 form in solution an equilibrium with the free ketone and the complex NbCl5 · PPh3. The chloride ion of 4-10 is perhaps coordinated to the metal.
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    Multistep Redoxsystems, LX. 1,4,5,8-Tetraoxo-1,4,5,8-tetrahydrothianthrene: Synthesis, Structure, and Spectroelectrochemical Properties (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 465-471 
    Details
    ISSN: 0009-2940
    Keywords: Thianthrene derivatives ; X-ray analysis ; MO calculation ; Cyclovoltammetry ; UV-Vis spectroelectrochemistry ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis, structure, cyclovoltammetric and spectroelectrochemical data of 1,4,5,8-tetraoxo-1,4,5,8-tetrahydrothianthrene (2a) are presented. A relation between the positive partial charge at the sulfur atom and the dihedral angle at the S—S axis is discussed on the basis of semiempirical MO calculations.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19931260226
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    Übergangsmetallaktivierte organische Verbindungen, XXXVIII. Chemoselektive nucleophile Methylierungen durch In-Situ-Blockierung von Aldehydgruppen unter α1-Phosphonioalkoxid-BildungHerrn Professor Ulrich Schöllkopf zum 65. Geburtstag gewidmet. (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 459-464 
    Details
    ISSN: 0009-2940
    Keywords: Chemoselectivity ; Titanium complexes ; Niobium complexes ; Tantalum complexes ; Methylation of aldehydes and ketones ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transition Metal-Activated Organic Compounds, XXXVIII[1].  -  Chemoselective Nucleophilic Methylation Reactions by In-Situ-Blocking of Aldehyde Groups by α1-Phosphonioalkoxide FormationHerrn Professor Ulrich Schöllkopf zum 65. Geburtstag gewidmet.For the selective methylation of a keto group in the presence of an aldehyde group the complex MeTiCl3·PPh3 and especially the reagent system [TiC]4·PPh3 + 0.5 Me2Zn] proved to be favourable. For instance, 6-oxoheptanal (8) was methylated by [TiCl4·PPh3 + 0.5 Me2Zn] at the keto group with 89% yield and 99:1 selectivity, whereas it was methylated by [TiCl4 + 0.5 Me2Zn] at the aldehyde group with 81% yield and 96:4 selectivity. A selective methylation of benzaldehyde in the presence of heptanal was achieved with MeNbCl4·PPh3 or [NbCl5·PPh3 + 0.75 Me2Zn] to give (1-chloroethyl)benzene (14; yield 92 or 53%; selectivity in each case 93:7) or with [TaCl5·PPh3 + 1.5 Me2Zn] to give mainly 1-phenylethanol (15) besides 16. A 96:4-selective benzylation (yield 74%) of a ketone in the presence of an aliphatic aldehyde was possible with [TiCl4·PPh3 + 1 PhCH2MgBr].  -  The high chemoselectivity is caused by irreversible blocking of aliphatic aldehyde groups by α1-phosphonioalkoxide formation[1], whilst the corresponding reaction of keto groups[1] and of benzaldehyde is reversible.
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    Silaheterocyclen, XXII. Diels-Alder-Reaktionen von Dichlor(neopentyl)silaethen mit Furanen und Umlagerung der erhaltenen Bicyclen zu monocyclischen Si - O-Siebenring-Verbindungen (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 575-580 
    Details
    ISSN: 0009-2940
    Keywords: Silaethene derivatives ; Furans ; Cycloaddition reactions ; Rearrangements ; Sila heterocycles ; Diels-Alder reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sila Heterocycles, XXII[1]. - Diels-Alder Reactions of Dichloro(neopentyl)silaethene with Furans and Rearrangement of the Resulting Bicycles into Monocyclic Si - O Seven-Membered Ring compoundsThe reaction of trichloro(vinyl)silane (1) and LitBu (2) initially leads to the α1-lithio adduct Cl3SiCH(Li)CH2tBu (3) which can be trapped by trimethylsilyl triflate yielding the C1-silylated product [Cl3SiCH(SiMe3)CH2tBu (5)]. 1,2-LiCl elimination from 3 gives dichloro(neopentyl)silaethene [Cl2Si=CHCH2tBu (4)] as intermediate. This can be established by insertion of 4 into the Si - O bond of Me3SiOMe to Cl2Si(OMe)CH(SiMe3)CH2tBu (6). 4 is a dienophile of high activity and reacts with the furans 7 - 9 to give the [4 + 2] cycloaddition compounds 10 - 12. These Diels-Alder products are thermally unstable and decompose slowly at room temperature into the starting furans and tetrachlorodisilacyclobutane (15). Under thermolysis conditions (3 d/17°C) they rearrange into the monocyclic Si - O seven-membered ring compounds 16 - 18. A mechanism for the 7-Oxa-2-silabicyclo[2.2.1]hex-5-en → 1-Oxa-2-silacyclohepta-4,6-diene rearrangement is proposed.
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    (Diphenylphosphanyl)(tetramethylcyclopentadienyl)thallium(I) (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 591-594 
    Details
    ISSN: 0009-2940
    Keywords: Indium(I) complexes ; Thallium(I) complexes ; Cyclopentadiene, (diphenylphosphanyl)tetramethyl- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (Diphenylphosphanyl)(tetramethylcyclopentadienyl)thallium(I)(Diphenylphosphanyl)tetramethylcyclopentadiene (1) reacts with TlOC2H5 to form Tl[C5Me4PPh2] (2). In a transmetallation reaction 2 reacts with InCl to yield the corresponding In[C5Me4PPh2] complex (3). The 1H-, 13C-NMR-and mass spectra as well as the single-crystal X-ray structure analysis of the monomeric 2 are reported and discussed.
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    URL: http://dx.doi.org/10.1002/cber.19931260307
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    Silaheterocyclen, XXIII. Synthese und Thermolyseverhalten von Si-funktionellen 2-Silaazetidinen (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 581-589 
    Details
    ISSN: 0009-2940
    Keywords: Silene, dichloroneopentyl- ; Imines ; Cycloaddition reactions ; 2-Silaazetidines ; Thermolysis reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Silaheterocycles, XXIII[1]. - Synthesis and Thermolysis Reactions of Si-Functionalized 2-SilaazetidinesDichloroneopentylsilene (1) is formed in situ by the reaction of trichlorovinylsilane with LitBu. The [2 + 2] cycloaddition to imines yields Si, Si1-dichloro-functionalized 2-silaazetidines in a preparative scale. With aldimines as trapping agents for 1, the resulting SiN four-membered ring compounds are isolated as syn/anti1-isomers (e.g. syn/anti-15 and -16; syn/anti ≍ 2:1). Silene 1 is not liberated from the silaazetidines on heating, but the Si, Si1-dichloro-substituted silanimine Cl2Si=NtBu (24) is formed. This can be trapped by Me3SiOMe or Ph2C=NtBu to give the addition products 25 and 26, respectively. The pathways are discussed which lead to stereoisomeric SiN ring compounds by a multiple-step mechanism including zwitterionic intermediates (1,4-dipoles). In addition there is strong evidence for the formation of 1, depending on the trapping reagent used. This fact may be explained by donor→silene interactions. The thermolysis products of silaazetidines support the formulation of a stepwise decomposition to an alkene and Cl2Si=NR derivatives.
    Additional Material: 4 Tab.
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    Kooperative Wirkung in π1-Ligand-verbrückten Zweikernkomplexen, XIII. Unerwartet schwache d-d-Wechselwirkungen in synfacialen heterodinuklearen μ1-Cyclooctatetraenkomplexen vom Typ {(CpCr)[(CO)3M′]}μ1-Cot (M′=Fe, Cr, W) (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 553-563 
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    ISSN: 0009-2940
    Keywords: Heterodinuclear cyclooctatetraene complexes ; Paramagnetism ; ESR of electron spin doublet and of electron spin quartet ; Redox properties ; d-d Interactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cooperative Effects in π1-Ligand-Bridged Dinuclear Complexes, XIII[1]. - Unexpected Weak d-d Interactions in Synfacial Heterodinuclear μ1-Cyclooctatetraene Complexes of the Type {(CpCr)[(CO)3M′]}μ1-Cot (M′=Fe, Cr, W)The heterodinuclear complexes {(CpCr)[(CO)3M′]}μ1-Cot (Cot=C8H8; M′=Fe, Cr, W) (5 - 7) and {(Cp*Cr)[(CO)3Cr]}μ1-Cot (Cp*=C5Me5) (9) are synthesized by the reaction of the corresponding mononuclear Cot complexes CpCr(η61-Cot) (4) and Cp*Cr(η61-Cot) (8), respectively, with M′(CO)3(EtCN)3 (M′=Cr, W) and with Fe2(CO)9. The CrFe compound 5 is obtained in very low yield only. However, much better yields of 5 are achieved in the reaction of CrCl2 and CrCp2 with (CO)3Fe(η41-Cot) (10) in the presence of an excess of Zn. X-ray structure determinations of 5 and 6 reveal synfacial configurations of the CpCr and M′(CO)3 units with a μ1-η5:3- and μ1-η4:51-Cot bonding mode for 5 and 6, respectively. The metal - metal distances are 2.9369(13) Å for 5 and 2.81(2) Å for 6 indicating metal - metal single bonds. 5 contains 33 valence electrons (ve) and is paramagnetic with one unpaired electron. A well-resolved fluid-solution ESR spectrum of 5 shows a 53Cr and 1H hyperfine structure (hfs). The 1H hfs can be calculated with three different 1H hyperfine coupling constants (1H hfcc) indicative of protons in α1-position with respect to the paramagnetic metal center: one 1H hfcc of the five Cp protons (1.68 G), one of three (3.32 G) and one of two protons of the Cot ligand (5.04 G). This agrees with the Cot bonding mode of the CpCr unit in the crystalline phase. The ratio of 3:2 protons for the Cot ligand prove the rigidity of the Cot ligand on the ESR time scale. The excellent agreement of the ESR data of the liquid and frozen solution ESR spectra of 5 with the ESR data of the mononuclear complex CpCr(η61-Cot) leads to the conclusion that the unpaired electron in 5 must predominantly be chromium-centered. 6, 7, and 9 have 31 ve and are paramagnetic with three unpaired electrons as shown by means of ESR spectroscopy and magnetic measurements. The calculations of the quartet ESR spectra of 6, 7, and 9 reveal zero-field splitting parameters D ranging from 3.6 to 4.8 cm-1 which are similar to that of the mononuclear quartet compound vanadocene. The small range in the parameters D prove the minor influence of the second metal on going from Cr to W. Hence, the three unpaired electrons are assumed to be mainly localized on the Cr center of the CpCr unit. Cyclic voltammetry studies result in the redoxcascade - 2 ⇄ - 1 ⇄ 0 ⇄ + 1 for 5 and 7 at +20°C and for 6 at -35°C. However, at +20°C 6 and 9 only show one electrochemically reversible reduction wave 0/-1, whereas the oxidation 0/+1 and the second reduction -1/-2 are irreversible. The redox potentials indicate a considerable influence of the metal combinations. On the strength of the ESR spectroscopic results and according to the results of crystal structure determinations, an isolobal relationship is drawn between the (CO)3M′(η8 - ×1-Cot) fragment and a cyclic organic π1-ligand with the hapticity × + 1.
    Additional Material: 7 Ill.
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    Reactions of cis1-Stannyl-boryl-alkenes with Sulfur Bis(trimethylsilylimide) and N1-Sulfinyl(trimethylsilyl)amine - X-ray Analysis of an 1-Amino-1λ41-thia-2-azonia-3-borata-1,4-cyclopentadiene (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 595-599 
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    ISSN: 0009-2940
    Keywords: cis1-Stannyl-boryl-alkenes ; Sulfur bis(trimethylsilylamide) ; N1-Sulfinyl(trimethylsilyl)amine ; NMR, multinuclear ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New heterocyclic systems (1-amino-1λ41-thia-2-azonia-3-borata-1,4-cyclopentadienes 4a and 4b, a 1λ41-thia-2-aza-3-bora-1-cyclopentanone 7 and a 1-trimethylstannyloxy-1λ41-thia-2-azonia-3-borata-1,4-cyclopentadiene 8) are formed by reaction of (E)1-2-diethylboryl-1-trimethylstannyl-1-butene (1a) and (E)1-3-diethylboryl-2-trimethylstannyl-2-pentene (1b) with sulfur bis(trimethylsilylimide) (2) and N1-sulfinyl(trimethylsilyl)amine (3). There is a marked influence of other substituents at the C=C bond on the product distribution. It appears that all reactions proceed via an intermediate borane adduct A. In A the proximity of the electrophilic site of 2 or 3 to various reactive sites of the alkene derivative opens the way to the final products. The proposed structures are supported by consistent 1H-, 11B-, 13C-, 29Si-and 119Sn-NMR data. In the case of compound 4a an X-ray analysis has been carried out.
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    URL: http://dx.doi.org/10.1002/cber.19931260308
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    Synthesis and Molecular Structure of Heterocycles Containing two Phosphorus(V) Centers Bridged by Two-Coordinate Phosphorus and Arsenic (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 601-604 
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    ISSN: 0009-2940
    Keywords: Arsenic, two-coordinate ; Phoshorus, two-coordinate ; Phosphinines ; Phosphabenzenes ; Arsadiphosphabenzenes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,1-Bis[(diphenylphosphanyl)methyl]ethene (3) reacts with PCl3 or AsCl3 in the presence of SnCl2 as a reducing agent to form cationic heterocycles in which the two newly generated phosphonium centers are bridged by two-coordinate, negatively charged phosphorus (4a) or arsenic (4b) centers. Hexachlorostannate(IV) dianions function as counterions to these heterocycles, in which the exocyclic methylene group is retained. By treatment of 4a with a base a rearrangement is induced which includes a proton migration from an endo-to the exocyclic CH2 group to give 5-methyl-1,1,3,3-tetraphenyl-1λ5,2λ3,3λ51-triphosphinine (5), a novel 1,2,3-triphosphabenzene species. The reaction of the arsenic compound 4b with base did not yield the corresponding arsa-diphosphabenzene, but gave only decomposition products. Compound 4b · 0.5 CH3CN has been studied by X-ray crystallography. The six-membered heterocycle shows a chair conformation with an arsenic atom solely coordinated by two phosphorus atoms at roughly equal distances with a sharp angle P - As - P of only 93.0(1)°.
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    URL: http://dx.doi.org/10.1002/cber.19931260309
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    Preparation and Crystal Structures of Gold(I) Complexes of a Series of Benzenethiolates: Pair Formation by Gold-to-Gold Interactions of (Benzenethiolato)(triphenylphosphane)gold(I) (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 605-610 
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    ISSN: 0009-2940
    Keywords: Gold(I) complexes ; Gold(I) thiolates ; Thiolato complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chloro(triphenylphosphane)gold(I) reacts readily with benzenethiol C6H5SH and a series of sterically hindered (2,4,6-trialkylbenzene)thiols 2,4,6-R3C6H2SH in the presence of NEt3 to yield stable gold(I) complexes Ph3PAu(S - 2,4,6-C6H2R3) [R=H (1), Me (2), Et (3), iPr (4)]. The crystal structures of these complexes have been determined by single-crystal X-ray diffraction analysis. In all compounds the gold atoms are linearly two-coordinate with very similar bond lengths and angles. - While complexes 2 - 4 with bulky thiolate ligands are monomeric in the crystal lattice, complex 1 has been found to form pairs of molecules with intermolecular gold - gold contacts of 313.5(5) pm. The Mössbauer spectra of the complexes exhibit large isomer shifts (I.S.), ranging from 3.06 to 3.72 mm s-1, and quadrupole splittings (Q.S.), ranging from 7.90 to 8.68 mm s-1. These data can be attributed to the strong electron-donating properties of the benzenethiolate ligands. The gold - gold contacts in complex 1 lead to I.S. and Q.S. values which are slightly smaller than those of 2 - 4. The Au - S distances do not show a major influence of the S - Au - P pairing in complex 1 as compared to complexes 2 - 4.
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    Metal-Metal Bonding in Paramagnetic Chromium(III) Complexes - An MO-Theoretical Case Study (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 631-643 
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    ISSN: 0009-2940
    Keywords: Chromium(III) alkyls ; Paramagnetism ; Calculations, MO ; Metal - Metal bonding ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electronic structures of the edge-sharing bioctahedral chromium(III) dimers {C5H5Cr(CH3)(μ1-Cl)}2 (2) and {Me5C5Cr(CH3)(μ1-CH3)}2 (4* (Cp* derivative), 4 (Cp derivative)), the trinuclear complex {C5H5Cr(μ1-Cl)}3(μ1-CH) (3), and the face-sharing bioctahedral chromium(III) compounds {Me5C5Cr}2(μ1-CH2) (6*, 6) [{Me5C5Cr}2(μ1-CH3)3]+ (7*, 7) have been studied MO-theoretically by the extended Hückel method. Proceeding from 2 over 3 to 4*, or from 6* to 7* a 3-center/4-electron chloride or methylene bridge is replaced by a 3-center/2-electron methyl group (a methylidyne cap in the trimer). The 3c/2e bridges give rise to an increased metal - metal overlap population due to Cr - Cr bonding within the core levels. In the series of 2 - 3 - 4* this is accompanied by a decrease in the Cr - Cr distance (329 - 284 - 260 pm) and effective magnetic moment, μeff (2.53 - 2.05 - 1.53 μB per Cr at room temp.). The latter can be ascribed to an increased splitting within the chromium d-block because of the shorter metal-metal separation. The bioctahedra 6* and 7* feature even shorter Cr - Cr contacts than 4* (239 and 242 pm), primarily because of their face-sharing geometry. However, their effective magnetic moments (per Cr) are 2.33 and 1.32 μB at room temp. The high magnetic moment for 6* can be understood from the orbital interactions in the frontier orbital metal d block: A face-sharing bioctahedron shows one σ, two δ, and no π type overlap, while an edge-sharing bioctahedron (4) has σ, π, and δ interaction between the metals. In the former this destabilizes only σ* sufficiently to prevent occupation by electrons (leaving five orbitals for six electrons, possible spin multiplicities S=0, 1, 2) while for the latter both σ* and π* are destabilized beyond electron occupation (leaving four MOs for six electrons, possible spin multiplicities S=0, 1). 4*, 6* and 7* are unusual examples of metal - metal bonded complexes containing octahedral CrIII ions.
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    Übergangsmetall-Stannyl-Komplexe, 7. Darstellung von Carben-Komplexen (π1-Aromat)(CO)2CrCR2 durch Umsetzung der anionischen Stannyl-Komplexe [(π1-Aromat)(CO)2CrSnPh3]- mit R2CX2 oder [R2CX]Y (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 657-664 
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    ISSN: 0009-2940
    Keywords: Carbene complexes ; Stannyl complexes ; Chromium complexes ; Anionic complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transition Metal Stannyl Complexes, 7[1]. - Preparation of Carbene Complexes (π1-Arene)(CO)2CrCR2 by the Reaction of the Anionic Stannyl Complexes [(π1-Arene)(CO)2CrSnPh3]- with R2CX2 or [R2CX]YCarbene complexes (π1-arene)(CO)2Cr=CR2 are formed in substitution/elimination reactions from the anionic stannyl complexes K[(π1-arene)(CO)2CrSnPh3] [π1-arene=C6H6 (1a), 1,3,5-Me3C6H3 (1b), 1,2,4,5-Me4C6H2 (1c)] C6Me6 (1d) and organic dihalides R2CX2 containing activated C - X bonds or ionic halides [R2CX]Y. Bis(stannyl) complexes (π1-arene)(CO)2Cr(SnPh3)2 (3) and hydrido(stannyl)complexes (π1-arene)(CO)2Cr(H)SnPh3 are formed as byproducts due to the reaction of the eliminated Ph3SnCl with the anionic starting complexes or electron transfer reactions, respectively. The portion and ratio of the byproducts is largely influenced by the steric properties of both the (π1-arene)(CO)2Cr fragment and the organic halide. Pyridinylidene complexes 2) are only obtained from 2-chloro-N1-methylpyridinium tetrafluoroborat with 1a - c, but not with 1d. With the sterically less demanding halides [R2N=C(H)Cl]Cl [NR2=NMe2, (n=3, 4)] or 3,3-dichloro-1,2-diphenylcyclopropene the carbene complexes (π1-arene)(CO)2Cr=C(H)NR2 or are obtained with all employed π1-arene ligands.
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    Über die-Synthese und Molekülstruktur von CH3M(SiH3)3 (M=Si, Ge) (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 665-668 
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    ISSN: 0009-2940
    Keywords: 2-Isotetrasilanylsodium salt ; Trisilylgermyl(alkali metal) salt ; 2-Methylisotetrasilane ; Methyltrisilylgermane ; Electron diffraction ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Molecular Structure of CH3M(SiH3)3 (M=Si, Ge)A solution of 2-isotetrasilanylsodium (1a) was obtained in good yield from silane and sodium under special conditions. Methylation of 1a with methyl p1-toluenesulfonate yields 2-methylisotetrasilane (1b). The corresponding methyltrisilylgermane (2b) was synthesized via (K, Cs)Ge(SiH3)3 (2a) resulting from the reaction of cesium trichlorogermanide with KSiH3 followed by methylation. The molecular structures of 1a and 1b were determined by electron diffraction analyses.
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    Schwefel(IV)1-Verbindungen als Liganden, 19. Kationische Ruthenium-Sulfen-Komplexe: Synthese und Reaktionen. Kristallstrukturanalyse von [Cp*(Me3P)2Ru(CH2=SO2)]PF6 (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 679-684 
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    ISSN: 0009-2940
    Keywords: Ruthenium complexes ; Sulfur dioxide complexes ; Sulfene complexes ; Nucleophilic addition ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sulfur(IV) Compounds as Ligands, 19[1]. - Cationic Ruthenium-Sulfene Complexes: Synthesis and Reactions. Crystal Structure Analysis of [Cp*(Me3P)2Ru(CH2=SO2)]PF6Methylene addition to coordinated sulfur dioxide yields the novel η2(C, S) sulfene complexes [Cp(dppm)Ru(CHR=SO2)]PF6 (R=H:3, Me: 4) and [Cp*(Me3P)2Ru(CH2=SO2)]PF6 (5). An X-ray structure determination of 5 reveals a relatively short C - S bond (167.5 pm). The sulfene complexes are powerful carbon electrophiles as shown by the rapid addition of halides, pseudohalides, amines, including „nonnucleophiles“ such as ethyldiisopropylamine and DBU, and phosphanes to 3. The regioselectivity of the reaction of 3 with enamines is opposite to that of free sulfene, i.e. coordination of the sulfene to ruthenium effects umpolung.
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    Vinyliden-Übergangsmetallkomplexe, XXII. Alkin-, Alkinyl(hydrido)1-, Vinyliden-und Vinylvinyliden-Komplexe des Rhodiums aus OH-, NH2- und Cl-funktionalisierten Alkinen (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 669-678 
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    ISSN: 0009-2940
    Keywords: Vinylidenerhodium complexes, γ1-functionalized, generation from alkynols and their derivatives ; (Vinylvinylidene)1- and allenylidenerhodium complexes, formation by HX elimination ; Alkynyl(hydrido)1- rhodium(III) complexes, preparation from alkyne or vinylidene precursors ; Rhodium complexes, cyclopentadienyl, with vinylvinylidene ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Vinylidene Transition Metal Complexes, XXII[1]. - Alkyne, Alkynyl(hydrido)1-, Vinylidene-, and Vinylvinylidene Complexes of Rhodium from OH-, NH2-, and Cl-Functionalized Alkynes
    Notes: The reaction of [RhCl(PiPr3)2]n with γ1-functionalized 1-alkynes HC≡C-CRR′X (X=OH, OMe, Cl, NH2) at room temperature leads to the formation of either alkyne-, alkynyl(hydrido)1-, or vinylidenerhodium complexes. The alkyne and alkynyl-(hydrido) derivatives rearrange thermally or in the presence of deactivated Al2O3 to the isomeric vinylidenerhodium compounds in almost quantitative yield. On treatment of the γ1-functionalized vinylidenerhodium complexes trans-[RhCl(=C=CH-CRR′X)(PiPr3)2] with Al2O3 or traces of acids, elimination of HX occurs and (for R=H, CH3; R′=CH3; X=OH, Cl, NH2) the (vinylvinylidene)rhodium compounds trans-[RhCl(=C=CH-CR=CH2)(PiPr3)2] are formed. In contrast, the reaction of trans-[RhCl(=C=CHCPh2OH)(PiPr3)2] with either Al2O3 or acid gives the allenylidene complex trans-[RhCl(=C=C=CPh2)(PiPr3)2]. The 1-hexyne derivatives HC≡C[CH2]3CH2X (X=OH, Cl) react with [RhCl(PiPr3)2]n to give alkyne-, alkynyl(hydrido)1-, and vinylidenerhodium compounds; attempts to form the cyclic vinylidene complex trans- by HX elimination from trans-[RhCl(=C=C=CH[CH2]3CH2X)(PiPr3)2] (X=OH, Cl) failed. The half-sandwich-type (vinylvinylidene)rhodium compounds [C5H5Rh(=C=CH-CR=CH2)(PiPr3)] (R=H, Me) are obtained from [RhH(C≡C-CR=CH2)Cl(py)(PiPr3)2] and NaC5H5.
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    (Bicyclo[3.2.0]hepta-1,3-dienyl)cobalt(I) Complexes (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 713-724 
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    ISSN: 0009-2940
    Keywords: Bicyclo[3.2.0]hepta-1,3-dienyl complexes ; Calculations, semiempirical ; Alkyne trimerization ; Cobalt complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three isomeric bicyclo[3.2.0]heptadienes 1 - 3 are compared by semiempirical calculations. Experimental attempts directed to the synthesis of derivatives of 1 are described. The synthesis, properties and some reactions of (η51-bicyclo[3.2.0]hepta-1,3-dienyl)(η41-cycloocta-1,5-diene)cobalt(I) (22), including an X-ray crystal structure determination of the reaction product with diphenylethyne, the tetraphenylcyclobutadiene complex 30, are presented.
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    URL: http://dx.doi.org/10.1002/cber.19931260323
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    Ein L3ZnOH-Komplex als funktionelles Modell des Enzyms Carboanhydrase (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 703-710 
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    ISSN: 0009-2940
    Keywords: Pyrazolylborate ligand ; Zinc hydroxide complex ; Enzyme model ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An L3ZnOH Complex as a Functional Model of the Enzyme Carbonic AnhydraseThe tridentate ligand hydrotris(3-tert1-butyl-5-methylpyrazolyl)borate (L3) reacts with zinc perchlorate hexahydrate to form L3ZnOH (1) which is the first mononuclear neutral zinc hydroxide complex. 1 is a structural model of the enzyme carbonic anhydrase due to its tetrahedral coordination with three N-heterocycles and one OH ion as ligands. Its functional analogy to the enzyme involves (a) reversible uptake of CO2 forming the unstable bicarbonate complex L3ZnOCOOH (4) in solution from which the dinuclear carbonate complex L3ZnOC(O)OZnL3 (3) crystallizes, (b) reaction with dialkyl pyrocarbonates forming the complexes L3ZnOC(O)OR (5) which are stable esters of the bicarbonate complex and which are easily hydrolyzed to ROH, CO2, and L3ZnOH, (c) thermal decarboxylation of the ethyl carbonate complex 5b resulting in the ethanolate complex L3ZnOEt (6) which is extremely sensitive to hydrolysis, (d) “inhibition” by small anions due to conversion of 1 into the complexes L3ZnX (7; X=Cl, CN, N3, OAc). The identity of the various L3Zn derivatives is established by NMR methods and structure determinations.
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    URL: http://dx.doi.org/10.1002/cber.19931260322
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    Nucleophile Singulett-Carbene in der [4 + 1]1-Cycloaddition mit 1,2,4,5-Tetrazinen: Eine neue Isopyrazol-Synthese (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 733-738 
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    ISSN: 0009-2940
    Keywords: Singlet carbenes ; [4 + 1] Cycloadditions ; Isopyrazoles ; Diels-Alder reactions ; [4 + 2] Cycloreversion ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nucleophilic Singlet Carbenes in the [4 + 1] Cycloaddition with 1,2,4,5-Tetrazines: a New Synthesis of IsopyrazolesA series of 3,6-disubstituted 1,2,4,5-tetrazines 6, including C6H5, SCH3, SO2CH3, N(CH3)2, CF3, CO2CH3 groups, has been submitted to [4 + 1] cycloaddition with the nucleophilic singlet carbenes 4, 15, and 20, which are generated from the precursors 1, 11 and 19, resp. In all cases isopyrazoles (4H1-pyrazoles) 9, 10, 18, and 21 are isolated in good yields. They are formed in a two-step reaction sequence with the [4 + 1] cycloadducts of type 8 as intermediates which eliminate nitrogen by subsequent [4 + 2] cycloreversion. The acceptor-substituted isopyrazole 9e is characterized as an electron-deficient diene by some Diels-Alder reactions with inverse electron demand leading to the expected azo-bridged cycloadducts 23, 25, 27, 29, and 31 without acid catalysis or application of higher pressure. With cyclooctyne (32), the [4 + 2] cycloaddition is followed by a [4 + 2] cycloreversion with formation of the cyclopentacyclooctene 34.
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    URL: http://dx.doi.org/10.1002/cber.19931260325
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    Phosphanalkylene, 53. Synthese von α,β1-ungesättigten Cycloalkanonen aus Bis[(1-acylalkyliden)1-triphenylphosphoranen] - Eine Methode zur Überführung von Carbonsäure-Anhydriden in carbocyclische und heterocyclische VerbindungenHerrn Professor Dr. Ulrich Schöllkopf zum 65. Geburtstag gewidmet. (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 725-731 
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    ISSN: 0009-2940
    Keywords: Phosphonium ylides ; Wittig reactions, intramolecular ; Aldol condensations, intramolecular ; 2-Cycloalken-1-ones ; 2-Cycloalkene-1,4-diones ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phosphane Alkylenes, 53[1]. - Synthesis of α,β1-Unsaturated Cycloalkanones from Bis[(1-acylalkylidene)triphenylphosphoranes] - A Method for the Transformation of Acid Anhydrides into Carbocyclic and Heterocyclic CompoundsAlkaline hydrolysis of bis[(1-acylalkylidene)triphenylphosphoranes] 3 leads to 2-cycloalken-1-ones 6. Intramolecular Wittig reaction of an intermediately formed monoacyl ylide 4 and intramolecular aldol condensation of a diketone 5, resulting from hydrolysis of both ylide functions, are discussed as possible reaction mechanisms. The oxidation of 3 with H2O2 · Ph3PO yields 7- and 8-membered 2-cycloalkene-1,4-diones 12, presumely via mono ylides 11 carrying an aldehyde group in the Ō-position. The reactions of 3 with aldehydes (molar ratio 1:1) lead to the formation of mono Wittig compounds 15 which can cyclize affording 5- and 6-membered 3-alkenyl-2-cycloalken-1-ones 16. Since the ylides 3 are easily available from acid anhydrides the reaction sequences represent versatile approaches for the transformation of acid anhydrides into 2-cycloalken-1-ones.
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    Tin for Organic Synthesis, 7. New Regioselective Syntheses of Diaryl Sulfones, Arenesulfonamides, and Arenesulfonic Acid Sodium Salts (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 763-768 
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    ISSN: 0009-2940
    Keywords: Aromatic substitution, electrophilic ; Sulfones, synthesis of ; Sulfonamides, synthesis of ; Sulfonic acids, sodium salts, synthesis of ; Stannanes, trialkylaryl-, application of ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of (trialkylstannyl)arenes 1 with corresponding reagents containing a chlorosulfonyl group leads, by exclusive ipso substitution, to important diaryl sulfones 2a - i, N1-alkyl-arenesulfonamides 8a - f, and sodium arenesulfonates 13a - c in high yields under mild conditions. The specific leaving ability of the stannyl group allows, moreover, the preparation of arylsulfonyl isomers which are not accessible under the influence of the conventional directing forces of substituents. With N, N1-dialkylamidosulfonyl chloride/AlCl3 complexes no destannylation takes place, but the first intramolecular sulfonyltin complex 11 is formed. This result is used to discuss details of the mechanism involved.
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    URL: http://dx.doi.org/10.1002/cber.19931260329
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    (E, Z)1-Equilibria, 17 Demonstration of the Nitrogen Inversion Mechanism of Imines in a Schiff Base ModelDedicated to Professor Heinrich Nöth on the occasion of his 65th birthday. (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 747-754 
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    ISSN: 0009-2940
    Keywords: Diastereotopomerization, (E, Z) ; Imines ; Inversion, nitrogen ; Permethylation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Experimental differentiation between pure C=N double bond rotation and nitrogen inversion in N1-arylimines is possible with a single compound (13b) under the proviso of slow rotation about the N-aryl single bond. Labelling by 1H and 13C nuclei at the diastereotopic faces of the C=N moiety as well as of the N-aryl group is the clue to a successful stereodynamic analysis, as performed by variable-temperature NMR spectroscopy of 13b, a sterically congested and chiral model compound. Interpretation of similar measurements on a second model (13d) is less straightforward. The experimental observation of time-averaged Cs symmetry by NMR coalescences is only compatible with a mechanism of (E/Z) stereomutation either by pure inversion at sp2 nitrogen or by a contribution from C=N rotation together with a synchronized (geared) controtation about the N-aryl single bond. However, the latter combination is concluded to be predominantly inversion-like by comparisons with related imines.
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    A Cholestenyl-Substituted Bis(indenyl)zirconocene-Derived Homogeneous Ziegler Catalyst for Stereoselective Propene Polymerization (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 755-761 
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    ISSN: 0009-2940
    Keywords: Zirconocene, chiral, non-bridged ; Polymerization, stereoselective ; Polypropylene, isotactic ; Enantiomorphic site control ; Zirconium complexes ; Ziegler catalyst ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (-)1-5-Cholesten-3β1-yl tosylate (6) undergoes SN2 substitution with indenyllithium to give (-)1-3-(5-cholesten-3α1-yl)indene (7), which is subsequently deprotonated by methyllithium to give the cholestenyl-substituted indenyllithium reagent 8. Its reaction with 0.5 molar equivalents of ZrCl4(THF)2 furnished the three bis[3-(5-cholesten-3α1-yl)indenyl]ZrCl2 diastereoisomers in a ratio of 9a: 9b: 9c=60 : 16 : 24. The major organometallic reaction product 9a was recovered isomerically pure and used for the generation of an active homogeneous metallocene/alumoxane Ziegler-type catalyst for stereoselective propene polymerization. The catalyst derived from the non-bridged chirally substituted bis(indenyl)zirconocene complex 9a produces partially isotactic polypropylene almost completely by enantiomorphic site control in the temperature range from - 50 to + 15°C.
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    URL: http://dx.doi.org/10.1002/cber.19931260328
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    Umlagerungen von 1- und 2-Cyan-2-norbornyl-Kationen (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 739-746 
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    ISSN: 0009-2940
    Keywords: Carbocations, destabilized ; Solvolysis ; Wagner-Meerwein rearrangement ; 6,2-H Shifts ; Ring Expansion ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Rearrangements of 1- and 2-Cyano-2-norbornyl Cations
    Notes: Sulfonates of exo-2-hydroxynorbornane-endo-2-carbonitrile (2c-e) were found to rearrange exothermally to give sulfonates of exo-2-hydroxynorbornane-1-carbonitrile (6c-e), solvolysis being a minor side reaction. In contrast, the analogous endo substrates (3c-e) afforded the rearranged alcohol 6a and tricyclo[2.2.1.02,6]heptane-1-carbonitrile (4) as the major products. We have not been able to trap 2-cyano-2-norbornyl cations by external nucleophiles or by internal 6,2-shifts of hydrogen or carbon. On the other hand, there is good evidence for the generation of 1-cyano-2-norbornyl cations from both 3d, e and 6e. The degenerate 6,2-H shift in these species has been uncovered by means of labeled or optically active precursors. The 1-CN substituent clearly promotes the 6,2-H shift relative to the parent 2-norbornyl cation, but is inferior to 1-C2F5. Ring expansion of a spiroannelated cyclopropane, involving a 6,2 shift of carbon, was also observed (25, 26 → 27, 28). Our data strongly suggest that 2-cyano-2-norbornyl cations are less stable than 1-cyano-2-norbornyl cations. The reaction rates of 2c versus 6c do not reflect the stability of the incipient carbocations, owing to the large difference in ground state energy.
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    URL: http://dx.doi.org/10.1002/cber.19931260326
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    Cycloadditionen von Benzothiet und aromatischen Nitroso-Verbindungen (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 775-778 
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    ISSN: 0009-2940
    Keywords: Hetero Diels-Alder reactions ; Regioselectivity ; Ring contraction ; Molecular dynamics ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cycloaddition Reactions of Benzothiete and Aromatic Nitroso CompoundsThe new heterocyclic ring systems 4H-3,1,2-benzoxathiazines 4 and 2,3-dihydro-1,2-benzothiazol 1-oxides 6 can be synthesized by cycloaddition of benzothiete (1) and aromatic nitroso compounds 3. The regioselectivity of the primary step and the secondary thermal or acid-catalyzed rearrangements are discussed.
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    URL: http://dx.doi.org/10.1002/cber.19931260331
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    (Ether-phosphan)eisen(II)1-Komplexe mit den Koordinationszahlen Vier, Fünf und Sechs (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 889-893 
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    ISSN: 0009-2940
    Keywords: Iron(II) complexes ; Ether phosphanes ; Coordination numbers ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (Ether-phosphane)iron(II) Complexes with the Coordination Numbers Four, Five, and SixPhotolysis of cis,cis,trans1-Br2(OC)2 Fe(P∑O)2 (1a, b) [O,P=Ph2PCH2CH2OCH3 (a), Ph2PCH2C4H7O (b)] results in the formation of the iron(II) complexes Br2Fe(P∼O)2 (2a), [BrFe-(P∩O)(μ1-Br)]2 (4b), and [trans1-Br2Fe(P∩O)(μ1-CO)]2 (5a) with the coordination numbers four, five, and six, respectively. 2a crystallizes in the triclinic space group P\documentclass{article}\pagestyle{empty}\begin{document}$\bar{1}$\end{document} with Z=2 and has two monodentated O,P functions (P∼O: η1-P1-coordinated; P∩O:η2-O,P1-coordinated). The dimeric complex 4b with two O∩P-chelated ligands crystallizes in the orthorhombic space group Pbca with Z=4. 2a and 4b, which react under CO pressure to give the starting complexes 1a, b, are also accessible from the ether-phosphanes 3a, b and anhydrous FeBr2.
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    Metallkomplexe in Biologie und Medizin, VI. Darstellung und Kristallstruktur von (Penicillaminato-O,S,N)bismut(III)1-chlorid (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 895-898 
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    ISSN: 0009-2940
    Keywords: Bismuth complex ; Penicillamine ; Crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metal Complexes in Biology and Medicine, VI[1]. - Synthesis and Structure of (Penicillaminato-O,S,N)bismuth(III) ChlorideBismuth(III) oxychloride reacts with D-(-)1-penicillamine to form [D-(-)1-penicillaminato-O,S,N]bismuth(III) chloride (1), the solid state structure of which has been determined by single-crystal X-ray diffraction. The tridentate chelation of the metal center by sulfur, nitrogen, and oxygen atoms leads to the formation of five-membered rings. Due to interaction of bismuth with oxygen atoms of the carboxy groups, a polymeric two-dimensional structure results in the crystal lattice. Bismuth has a seven-fold inner coordination sphere.
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    Beiträge zur Chemie des Bors, 216. Über die Komplexbildung von 1,3,2,4-Diphosphadiboretanen mit Pentacarbonylchrom sowie über die Darstellung und Reaktivität von Borylidenphosphan-Komplexen (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 875-887 
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    ISSN: 0009-2940
    Keywords: 1,3,2,4-Diphosphadiboretanes, 2,4-bis(dialkylamino)- ; Boranes, (dialkylamino)bis(alkylphosphanyl)- ; Chromium, pentacarbonyl[2,3-bis(dialkylamino)1-1,3,2,4-diphosphadiboretane] complexes ; Chromium, pentacarbonyl[(2,2,6,6-tetramethylpiperidino)phosphane-P]- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Contributions to the Chemistry of Boron, 216[1]. - On the Complex Formation of 1,3,2,4-Diphosphadiboretanes with Pentacarbonylchromium and the Preparation and Reactivity of Borylidenephosphane Complexes2,4-Bis(dialkylamino)1-1,3,2,4-diphosphadiboretanes (R2NBP-CMe3)2 with sterically undemanding amino substituents are prepared together with the corresponding bis(phosphanyl)1-boranes R2NB(PHCMe3)2 by the reaction of R2NBCl2 with Li-P(H)CMe3. Complexes of 1,3,2,4-diphosphadiboretanes with one or two pentacarbonylchromium fragments were obtained by the reaction of the ligands with Cr(CO)5·THF or Cr(CO)5·NMe3. If substituents are sterically demanding, cycloreversion is observed with formation of [(aminoborylidene)1-phosphanyl-P]pentacarbonylchromium compounds tmpB=PR[Cr(CO)5] (10, 29) with an allene-like structure. Complex 29 may also be prepared by HCl elimination from tmp-B(Cl)-P(H)CMe3[Cr(CO)5] (34) with lithium diisopropylamide. This reaction can by reversed be the addition of HCl. The diphosphadiboretane 11 reacts with HCl, ethanol, and secondary amines with cleavage of all BP bonds. The X-ray structures of complexes (Et2NB - PCMe3)2[Cr(CO)5]2 (23) and (iPr2NB - PCEt3)2 [Cr(CO)5] (25) as well as of the diphosphadi-boretanes (Me2NB - PCMe3)2 (11) and (iPr2NB - PCEt3)2 (24) are presented. The intra ring angles of 23 remain almost unchanged upon complexation. In contrast, the B2P2 ring of 25 is slightly folded and its noncoordinated P atom approaches a planar environment.
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    Photoinduced Electron Transfer in Porphyrin-Quinone Cyclophanes, 8 Conformational Mobility and Crystal Structures of Porphyrin-Quinone Cyclophanes (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 811-821 
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    ISSN: 0009-2940
    Keywords: Porphyrin-quinone cyclophanes ; Photoinduced electron transfer ; Porphyrin cyclophanes, conformational mobility of, crystal structures of ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to correlate photoinduced electron-transfer in porphyrin-quinone cyclophanes to specific molecular conformations, the internal mobility of single-and double-bridged porphyrin-quinone cyclophanes was studied by low-temperature 1H-NMR measurements. The dynamic processes observed are discussed in terms of N-H/N tautomerisation, of the rotation of the rings in the bridges, and of a specific “swinging bridge” process back and forth between two equivalent unsymmetrical conformations with a tilted orientation of the porphyrin and quinone ring planes. For comparison with the conformational situation in solution the results of X-ray structure analyses of 3(X=OMe) and 6, as representative examples of single-bridged quinone-porphyrin cyclophanes, and of the corresponding tetramethoxybenzene-bridged octamethylporphyrin cyclophane 4(X=OMe) are reported and discussed. In contrast to the previously solved crystal structure of the quinone-porphyrin-quinone cyclophane 1(X=H), all three X-ray structure analyses of the single-bridged porphyrin cyclophanes proved the existence of unsymmetrical, tilted-plane structures similar to those discussed as the stable conformations in the “swinging bridge” process.
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    Pyrano[4,3-b]pyran-2,5-dione, 1. Einfache Synthese von Pyranopyrano-chinolintrionen (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 841-844 
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    ISSN: 0009-2940
    Keywords: 2H,5H1-Pyrano[4,3-b]pyrans, 2,5-dioxo- ; 2H,5H1-Pyrano[2′,3′:4,5]Pyrano[2,3-b]quinoline-2,5, 12-triones, 7,12-dihydro- ; 4H1-Pyrano[2,3-b]quinoline-4,5-diones, 5,10-dihydro- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrano[4,3-b]pyran-2,5-diones, 1. - Convenient Synthesis of Pyranopyrano-quinolinetrionesReaction of malondiamides 1 with malonyl chloride (5) leads to 2,5-dioxo-2H,5H1-pyrano[4,3-b]pyrans 7, which readily react with diazomethane to give the corresponding methyl ethers 8. Thermically induced cyclisation of 8 affords 7,12-dihydro-2H,5H1-pyrano[2′,3′ :4,5]pyrano [2,3-b]quinoline-2,5,12-triones 9. Acidic hydrolysis of 9 yields 4H1-pyrano[2,3-b]quinoline-4,5(10H)1-diones 10, while basic hydrolysis of 9 gives 4-hydroxy-2(1H)1-quinolinones 11.
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    Synthesis and Crystal Structure of the First “1,2-Diphospha[4]radialene” (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 845-847 
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    ISSN: 0009-2940
    Keywords: Hetero[4]radialene ; 1,2-Diphosphetane ; Butadiene, 2,3-bis(chlorophosphanyl)- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,2-Diphosphetane 4, the first “1,2-diphospha[4]radialene”, has been prepared in 83% yield by the reductive coupling reaction of 2,3-bis(chloroisopropylphosphanyl)butadiene 3a with lithium in THF. The X-ray crystal structure of 4 was determined, and it shows that 4 is a highly strained 1,2-diphosphetane.
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    Organosubstituierte 1,1′-Spirobisilole und 1,1′-Spirobigermole durch vierfache Organoborierung von Tetra-1-alkinylsilanen und -germanen (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1385-1396 
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    ISSN: 0009-2940
    Keywords: Silanes, tetra-1-alkynyl- ; Germanes, tetra-1-alkynyl- ; 1,1-Ethyloboration, intermolecular ; 1,1-Vinyloboration, intramolecular ; Spirosilanes ; Spirogermanes ; Protodeborylation ; Transition metals, η41-complexes of ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organosubstituted 1,1′-Spirobisiloles and 1,1′-Spirobigermoles by Fourfold Organoboration of Tetra-1-alkynylsilanes and -germanes[1]Si(C≡CR)4 [R=Me (A), R=Ph (B), R=SiMe3 (C)] and Ge(C≡CR)4 [R=Me (D), R=Ph (E)] react with Et3B by twofold intermolecular ethyloboration and twofold intramolecular vinyloboration to form the organo-substituted 5-sila(germa)spiro[4.4]nonatetraenes , R=Me: 1a, R=Ph: 1b; M=Ge, R=Me: 2d, R=Ph: 2e] via the mono-and bisethyloboration compounds 3 or 4 (e.g. 3b, 4c) with different rates: Ge 〉 Si; Me 〉 Ph. For comparison, compounds Sn(C≡CR)4 [R=Me (F), R=Ph (G)] react with Et3B in the absence of a solvent to mixtures of various spirotin compounds (5f, 5g, 6f, 8f, 9g, 10g, 11g) of which only 9g (R=Ph) corresponds to the spirosilanes and -germanes. This is the result of effective competition between intramolecular and intermolecular organoboration in the case of the tetra-1-alkynyltin compounds. The protodeborylation of 1a, b and 2d, e with MeCO2H leads to 12a, b and 13d, e, respectively. 12a isomerises by UV irradiation to allyl isomers 12a′. From 12a with 2 equiv. of maleic anhydride the 1:2 addition compound 14a is obtained, the autaddition of 12a, d leads to 15a, d. Spiro compound 12a reacts with (OC)5Fe or CpCo(C2H4)2 to give the cyclodiastereomeric η41-complexes [(OC)3Fe]2-12a (16a1-a4; X-ray structure analysis of meso- 16a1), (OC)3Fe-12a (17a) and (CpCo)2-12a (18a1-a4). - All products were characterized by multinuclear NMR, including measurements of the coupling constants 1J(13C13C), 2J(29Si29Si), nJ(29Si13C) and nJ(119Sn13C).
    Additional Material: 2 Ill.
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    Synthese und Struktur von [Rh2(μ1-NO)(μ1-H)(PiPr3)4]: Ein chiraler, NO-und Hydrid-verbrückter Rhodium(0)1-Zweikernkomplex (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1409-1411 
    Details
    ISSN: 0009-2940
    Keywords: Rhodium hydrido complexes ; Binuclear rhodium complex, molecular structure of ; NO and hydride as bridging ligands ; Axial chirality ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Structure of [Rh2(μ1-NO)(μ1-H)(PiPr3)4]: A Chiral, NO-and Hydride-Bridged Binuclear Rhodium(0) ComplexThe reaction of RhCl3 · 3 H2O, PiPr3, iPrONa / iPrOH and N1-methyl-N1-nitroso-4-tosylamide (diazald) yields the binuclear rhodium complex [Rh2(μ1-NO)(μ1-H)(PiPr3)4] (3) in 67% yield. 3 is probably formed via [RhH(PiPr3)3] (4) for which an improved preparative procedure is given. The X-ray structural analysis of 3 proves that two pairs of inequivalent phosphane ligands are present. In solution, 3 shows a fluctional behavior which is reminiscent to that of molecules possessing axial chirality.
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    URL: http://dx.doi.org/10.1002/cber.19931260620
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    (Di-tert1-butylfluorsilyl)hydrazin, ein Baustein für strukturisomere N,N- und N,N′1-Bis(silyl)hydrazineHerrn Professor Heinrich Nöth zum 65. Geburtstag gewidmet. (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1413-1416 
    Details
    ISSN: 0009-2940
    Keywords: Hydrazine, N-(fluorosilyl)- ; Condensation ; Cyclization ; Bis(silyl)hydrazines ; Isomerism, structural ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (Di-tert1-butylfluorosilyl)hydrazine, a Building Block for Structure-Isomeric N,N- and N,N′1-Bis(silyl)hydrazinesDi-tert1-butyldifluorosilane reacts with monolithiated hydrazine to give the stable monosilylated hydrazine 1 and the six-membered ring 2. The bis(fluorosilyl)hydrazine 3 is formed in a condensation reaction by heating 1 at 220°C. HCl elimination between 1 and chlorosilanes leads to the N,N′1-disubstituted hydrazines 4 and 5. An N,N′1-bis(silyl)hydrazine 6 is obtained in the reaction of lithiated 1 with difluorodiisopropylsilane while an N,N1-bis(silyl)hydrazine 7 is formed with tert1-butyltrifluorosilane. Structural isomerism (8-11) is observed in reactions of lithiated 1 with [(trifluorosilyl)amino]silanes.
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    URL: http://dx.doi.org/10.1002/cber.19931260621
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    Tri-, Tetramethylbullvalene und Hexamethylbibullvalenyl (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1419-1423 
    Details
    ISSN: 0009-2940
    Keywords: Cope rearrangement ; Bullvalenes, tri-, tetramethyl- ; Bibullvalenyl, hexamethyl ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tri-, Tetramethylbullvalenes and HexamethylbibullvalenylThe known monomethylbullvalenes 6 and dimethylbullvalenes 7 are supplemented by tri-8 and tetramethylbullvalenes 9 as well as the hexamethylbibullvalenyl 10. The isomer distributions of the methylbullvalenes 6-9 are determined by NMR-spectroscopy. A vicinal arrangement of two methyl groups is not found. The 4-, 6-, 10-positions are slightly preferred in respect to the 3-, 7-, 9-positions. In the case of the methylbullvalenes 8 and 9 methyl groups occupy additionally the 1-, 2-, 8- but not the 5-position. Contrary to tetrabromobullvalenes 5, isomers of 9 show no pronounced kinetic stability.
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    URL: http://dx.doi.org/10.1002/cber.19931260622
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    Carben-analoge Amidoosmium-Komplexe mit Os—N-Doppelbindung: Synthese, Struktur und Reaktivität von [(Mes)Os(=NHR)(PiPr3)]PF6Herrn Professor Heinrich Nöth zum 65. Geburtstag gewidmet. (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1403-1408 
    Details
    ISSN: 0009-2940
    Keywords: Cationic amido osmium(II) complexes, synthesis from dichloro metal precursor and primary amines ; Os-N double bond ; Aldimino(hydrido)osmium(II) complex, formation by β1-hydride migration ; Amino(chloro)osmium(II) complex, preparation by protonation of an amido derivate ; Dinuclear imidoosmium complex, presence of a Os2N2 four-membered ring ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carbene-Type Amidoosmium Complexes with an Os—N Double Bond: Synthesis, Structure and Reactivity of [(Mes)Os(=NHR)(PiPr3)]PF6*The reaction of [(Mes)Os(PiPr3)Cl2] (1) (Mes=1,3,5-C6H3Me3) with primary amines RNH2 (R=Ph, Me, Et) in acetone/water (1:1) gives, after addition of KPF6, the amidoosmium(II) complexes [(Mes)Os(=NHR)(PiPr3)]PF6 (2-4) in 60-80% yield. From 1 and Et2NH, the chloro(hydrido)compound [(Mes)1-OsH(PiPr3)Cl] (5) is formed. The X-ray structural analysis of 2 reveals that the geometry around the osmium atom is trigonalplanar (with the midpoint of the mesitylene ring as one coordination site) and that the Os—N distance of 1.923(4) Å is in agreement with an Os—N double bond. Thermolysis of 4 (R=Et) at 165°C leads to the formation of the aldimino(hydrido)osmium complex [(Mes)OsH(NH=CHMe)(PiPr3)]PF6 (6) by β1-hydride migration from the NCH2 carbon atom to the metal atom. Protonation of 3 (R=Me) with HCl gives the amine complex [(Mes)Os(NH2Me)(PiPr3)Cl]PF6 (7), whereas on treatment of 3 and 4 with CD3NO2 the deuterated derivatives [(Mes)Os(=NDR)(PiPr3)]PF6 ([D1]-3, [D1]-4) are almost quantitatively formed. Compound 2 (R=Ph) reacts with KOtBu by proton abstraction and phosphane elimination to give the dinuclear imidoosmium complex [(Mes)2Os2(μ1-NPh)2] (8).
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19931260619
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    Penta-und Hexabrombullvalene (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1425-1427 
    Details
    ISSN: 0009-2940
    Keywords: Cope rearrangement ; Bullvalenes, pentabromo-and hexabromo- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Penta-and HexabromobullvalenesThe Pentabromobullvalenes 2a-d and the hexabromobullvalenes 3a/b are synthesized and the corresponding isomers are identified. 2 constitutes an equilibrium of four isomers. The isomer 2a is separated from the mixture by column chromatography. For the kinetically most stable isomer 2a the half-life time for equilibration at 55°C amounts to ca. 30 h. Two non-equilibrating isomers 3a and 3b are isolated, however, in the case of hexabromobullvalene 3. The bullvalene-typical property of a fluxional structure is now practically no longer existent.
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    URL: http://dx.doi.org/10.1002/cber.19931260623
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    Mono-, Di-, Tri-, Tetra-, Penta-und Hexaphenylbullvalene (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1429-1433 
    Details
    ISSN: 0009-2940
    Keywords: Cope rearrangement ; Bullvalenes, mono-, di-, tri-, tetra-, penta-, and hexaphenyl- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mono-, Di-, Tri-, Tetra-, Penta-and HexaphenylbullvalenesLithium diphenylcuprate reacts with the corresponding bromobullvalenes to yield the phenylbullvalenes 1-6, whose substitution patterns are deduced from their 1H-NMR spectra. Starting with triphenylbullvalenes 3 some isomers show a relatively high kinetic stability which culminates in the case of the hexaphenylbullvalenes 6a and 6b in the loss of the phenomenon of fluctuating structure for the bullvalene skeleton.
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    URL: http://dx.doi.org/10.1002/cber.19931260624
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    Novel Spherand-Type Calixarenes - Synthesis, Conformational Studies, and Isomer Separation (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1435-1439 
    Details
    ISSN: 0009-2940
    Keywords: [1n]Metabiphenylophanes, hydroxy- ; Calixarenes ; Conformation ; Hydrogen bonding, intramolecular ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The novel macrocyclic compounds hexahydroxy[1.0.1.0.1.0]-6b and octahydroxy[1.0.1.0.1.0.1.0]metacyclophane 6c have been prepared in 50-70% yield by base-catalyzed condensation of 5,5′-di-tert1-butyl-2,2′-dihydroxybiphenyl (5) with formaldehyde in xylene. The conformations of trimer 6b and tetramer 6c have been evaluated from their dynamic 1H-NMR spectra. Methylation of the hydroxyl groups of 6b and 6c with MeI gives the corresponding methoxy[1n]metabiphenylophanes 7b and 7c in good yields. The metacyclophane 7b has been found to consist of two isomers, out of which one was separated pure. The structural characterization of these products is discussed.
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    From para1-Dimethoxybenzene Toward Crownbenzenophanes, 2. Synthesis, X-ray Structure and Fluorescence Emission Properties of 1,3,10,13,16,19,22-Heptaoxa(3,13)[28]paracyclophane and Its Complex with Sodium Cation (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1441-1446 
    Details
    ISSN: 0009-2940
    Keywords: Supramolecular chemistry ; Crown ethers ; Phanes ; Fluid solutions and single crystals, spectroscopic properties of ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and X-ray molecular structure of the title compound, an heptaoxa[3,13]paracyclophane, as well as that of its 1:1 sodium complex are described; a study of the absorption and fluorescence spectra indicates that this crown-cyclophane behaves as a hybrid between strained classical cyclophanes and large macrocycles.
    Additional Material: 7 Ill.
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    Bimolekulare Radikalbildung durch H-Transfer, 2. H-Transferreaktionen mit Phenalen (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1039-1045 
    Details
    ISSN: 0009-2940
    Keywords: Hydrogen transfer ; Radical formation, molecule induced ; C—H bond dissociation enthalpies, determination of ; Catalysis ; Coal pyrolysis ; Phenalene ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bimolecular Formation of Radicals by H-Transfer, 2[1]. - H-Transfer Reactions of PhenaleneThe uncatalysed H transfer from phenalane (7) to α1-methyl-styrene (2) and the selfreaction (d) of phenalene (7) are quantitative transformations in the presence of an excess of 9,10-dihydroanthracene (1) (DHA) in diphenyl ether at 200-250°C. In this system phenalene (7) is consumed only in reaction (d) because the phenalenyl radicals (9) are captured by DHA (1) to give phenalene (7) and 9,10-dihydroanthryl radicals (3). The latter disproportionate rapidly. Accordingly, phenalene (7) acts as a catalyst for the hydrogenation of α1-methylstyrene (2) by DHA (1). The activation parameters of the two reactions (e) and (d) were obtained from kinetic experiments between 200-250°C. They allow the determination of the C—H bond enthalpy δHdiss of phenalene (7) (65.3 kcal mol-1) at the methylene position.
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    Synthesis of Isomerically Pure Organodihydrofullerenes (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1061-1067 
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    ISSN: 0009-2940
    Keywords: Buckminsterfullerenes ; Organodihydrofullerenes ; Fullerene derivatives ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Controlled two-step nucleophilic hydroalkylations, hydroar-ylations as well as hydrostannylations of fullerene-60 (1) and fullerene-70 (2) lead to defined organodihydrofullerenes C60HR and C70HR. NMR investigations show that only one isomer of each organodihydrofullerene with Cs symmetry is formed. In all cases the addition takes place at a double bond separating two six-membered rings of the fullerene core. In this way a variety of organodihydrofullerenes also carrying functional groups have been synthesized.
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    Masthead (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/cber.19931260501
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    Oxidative Spaltung von Poly(o1-phenylendiselenid) (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1071-1076 
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    ISSN: 0009-2940
    Keywords: Selenium halogen compounds ; Poly(o1-phenylenediselenide), cleavage of ; Oxidative cleavage ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oxidative Cleavage of Poly(o1-phenylenediselenide)Poly(o1-phenylenediselenide) is cleaved at the Se-Se bond by treatment with SOCl2 to give benzene-1,2-bis(selenenyl chloride) (2) and benzene-1,2-bis(selenium trichloride) (3), respectively. In the solid state 2 is dimerized by Se…Se bonds whereas 3 is monomeric having terminal as well as intramolecular bridging Cl atoms. Treatment of 2 with SbCl5 gives an ionic compound (4) with a dimeric cation exhibiting a weak Se—Se bond and SbCl6- as a counterion 3 reacts with W(CO)6 to give trigonal prismatic dicarbonyl bis(o1-phenylenediselenolato)tungsten (5).
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    2,4,6,8-Tetraphenylbarbaralan - ein orangeroter, thermochromer Kohlenwasserstoff ohne Chromophor[1,2] (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1047-1060 
    Details
    ISSN: 0009-2940
    Keywords: Bicyclo[3.3.1]nonane, derivatives of ; 2-Oxatwistane, derivative of ; 2-Oxatricyclo[4.4.0.03,8]decane, derivative of ; Phenyllithium-cerium(III) chloride reagent ; 1,2-Addition to carbonyl groups ; Transannular reaction ; Dipotassium tetraphenylbicyclo[3.3.1]nonadienediide by deprotonation with butylpotassium ; Barbaralane, 2,4,6,8-tetraphenyl-, by oxidation of dipotassium tetraphenylbicyclo[3.3.1]nonadienediide with 1,2-dibromo-ethane ; Thermochromism ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2,4,6,8-Tetraphenylbarbaralane - an Orange-Red, Thermochromic Hydrocarbon Devoid of a Chromophore[1,2]The diphenylbicyclo[3.3.1]nonanedione 6 adds phenylcerium-(III) dichloride to afford a high yield of the triphenyl-2-oxa-twistanol 8. In contrast, phenyllithium yields a mixture of tri-phenylhydroxyketone exo-7, tetraphenylbicyclo[3.3.1]nona-nediol 9, and 8. The latter is dehydrated by sulfuric acid in acetic acid to produce the triphenylbicyclo[3.3.1]nonenone 10 in almost quantitative yield. Addition of phenylcerium(III) dichloride to 10 affords a 3:2 mixture of the tetraphenylbicy-clo[3.3.1]nonenols exo- and endo-11 which may be separated by chromatography. Dehydration of the mixture yields quantitatively the tetraphenyldiene 12. On treatment with an excess of butylpotassium in pentane, 12 is converted to the deep violet, crystalline dipotassium salt 17 which may be purified by reprecipitation from its tetrahydrofuran solution with pentane. When the solution of 17 in tetrahydrofuran is slowly added to an excess of 1,2-dibromoethane at -60°C, the dianion is immediately oxidized to produce the tetraphenylbarbara-lane 4 which is isolated in 30% yield as orange-red crystals after chromatography. - The structures of the new compounds are based on spectroscopic evidence and X-ray diffraction analyses of 4, 8, exo-11, and 12. The conformations in solution are inferred on the basis of vicinal proton coupling constants and a comparison with coupling constants calculated with the aid of the Karplus equation from torsional angles obtained by X-ray diffraction analyses. The conformation of exo-11 in solution closely resembles that present in the crystal. - While the barbaralane 4 exists as a pair of very rapidly rearranging degenerate valence tautomers in solution, the degeneracy is lifted in the crystal lattice. As a result, the crystal consists of two rapidly rearranging but non-equivalent valence tautomers in a ratio of 9:1 as estimated from the apparent atomic distance C2-C8 of 4 and the C2-C8 bond length of the model barbaralane 18. - The orange-red colour of 4 in the crystal and in solution results from a pronounced shoulder in the UV/Vis spectrum at 430 nm, the intensity of which strongly depends on the temperature. Thus, 4 is the first barbaralane which exhibits colour though it is lacking a classical long-wavelength chromophore.
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    Metallinduzierte und basenkatalysierte 2-Propinyl-Allenyl-Umlagerung in [(HC≡CCH2)(2,4,6-tBu3C6H2O)]P=MoCP(CO)2 (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1077-1080 
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    ISSN: 0009-2940
    Keywords: Molybdenum complexes ; Rearrangements, metal-induced, base-catalyzed ; Isomerizations, 2-propynyl-allenyl ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metal-Induced and Base-Catalyzed 2-Propynyl-Allenyl Rearrangement in [(HC≡CCH2)(2,4,6-tBu3C6H2O)]P=MoCP(CO)2The synthesis and reactivity of [(HC≡CCH2)(2,4,6-tBu31-C6H2O)]P=MoCp(CO)2 (3) is described. [(HC≡CCH2)(R)]PCl (1) reacts with NaMoCp(CO)3 (2) to afford the s̰3,λ41-phosphanediyl compounds 3. With NEt3 a prototropic rearrangement of the 2-propynyl ligand of 3 to an allenyl group in [(H2C=C=CH)(R)]P=MoCp(CO)2 (5) is observed. However, with Cr(CO)5 · THF a metal-induced rearrangement of the 2-propynyl unit in 3 yields η3-{(2,4,6-tBu3C6H2O)[(CO)5Cr]PCHC=CH2}MoCp(CO)2 (7). Complex 7 contains a 1-phosphaallyl system, which is functionalized by an exocyclic CC double bond X-ray structure analyses of 3 and 7 are performed.
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    Kohlenwasserstoffverbrückte Komplexe, XXVII. C - C-Kupplung von ungesättigten Kohlenwasserstoffen in anionischen und kationischen Komplexen. Addition der Anionen von μ1-(Diphenylmethan)1-, μ1-Fluoren-und μ1-(9,10-Dihydroanthracen)1-bis(tricarbonylchrom) an koordinierte Olefin-, Benzol-, Cyclohexadienyl-, Cycloheptadienyl-und Cycloheptatrienyl-Liganden (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1081-1089 
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    ISSN: 0009-2940
    Keywords: Chromium ; Molybdenum ; Tungsten ; Manganese ; Rhenium ; Iron ; Cobalt ; Diphenylmethane ; Fluorene ; 9,10-Dihydroanthracene ; Cyclohexadiene ; Cyclohexadienyl ; Cycloheptadiene ; Cycloheptatriene ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydrocarbon-Bridged Complexes, XXVII[1]. - C—C Coupling of Unsaturated Hydrocarbons of Anionic and Cationic Complexes. Addition of Anions from μ1-(Diphenylmethane)1-, μ1-Fluorene-, and μ1-(9,10-Dihydroanthracene)1-bis(tricarbonylchromium) to Coordinated Olefin, Benzene, Cyclohexadienyl, Cycloheptadienyl, and Cycloheptatrienyl LigandsHerrn Professor Herbert D. Kaesz zum 60. Geburtstag gewidmet.The addition of the anions 1 - 3 of μ1-(diphenylmethane)1-, μ1-fluorene-, and μ1-(9,10-dihydroanthracene)1-bis(tricarbonylchromium) to π1-bonded hydrocarbons (olefin, benzene, cyclohexadienyl, cycloheptadienyl, and cycloheptatrienyl) in cationic complexes of manganese, rhenium, iron, chromium, molybdenum, tungsten, and cobalt provides a synthesis of new hydrocarbon-bridged heterometallic complexes 4 - 10.
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    OsO3F2 and OsO2F4, Preparation and Crystal Structures (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1331-1336 
    Details
    ISSN: 0009-2940
    Keywords: Osmium difluoride trioxide, preparation, structure ; Osmium tetrafluoride dioxide, preparation, structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new method for preparing OsO3F2 is presented. Its crystal structure reveals a polymeric chain structure with distorted octahedral geometry for the OsO3F3 units and symmetrical, non-linear fluorine bridges. The OsO3F3 unit has a facial geometry. This structure is not in accord with predictions on the molecular structure of OsO3F2. OsO2F4, obtained from KrF2 and OsO4, crystallizes in the space group P61 forming a sixfold helical chain arrangement of nearly octahedral OsO2F4 molecules. Oxygen or fluorine atoms are partially disordered. The cis orientation of the two oxygen atoms is established by means of NMR, vibrational spectroscopy, and X-ray data.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19931260610
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  • 199
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    Electronic Resource
    Synthesis, X-Ray Structure and Complexation Behavior of the New Tripodal Phosphane Ligand cis, cis-1,3,5-Tris[(diphenylphosphanyl)methyl]1-1,3,5-trimethylcyclohexane (tdppmtmcy). Crystal Structure of Ir(tdppmtmcy)(CO)Cl (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1341-1346 
    Details
    ISSN: 0009-2940
    Keywords: Phosphane ligand, tripodal ; Iridium complex ; C—H activation, intramolecular ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The introduction of three methyl groups into the ipso positions of the cyclohexane ring in cis,cis-1,3,5-tris[diphenylphosphanyl)methyl]cyclohexane (tdppmcy) (1) leads to the new tripodal phosphane ligand cis,cis-1,3,5-tris(diphenylphosphanyl)methyl]1-1,3,5-trimethylcyclohexane (tdppmtmcy) (5). The dynamic behavior is studied by variable-temperature NMR spectroscopy and compared with the structure (X-ray analysis) in the solid state. Treatment of 5 with Ir(PPh3)2(CO)Cl gives 6 where the two PPh3 groups are replaced by two (diphenylphosphanyl)methyl groups of the ligand 5. In addition, an intramolecular C—H metalation takes place resulting in the oxidative addition of a ring methylene C—H bond to the metal. The X-ray structure of 6 is determined.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19931260612
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  • 200
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    Electronic Resource
    Synthesis of Macrocyclic Mercury(II) Derivatives of S,S′1-Trimethylene-and S,S′1-Tetramethylenebis(cis1-stilbene-α,β1-dithiol) with Unusual StructuresDedicated to Professor Klaus Hafner on the occasion of his 65th birthday. (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1337-1340 
    Details
    ISSN: 0009-2940
    Keywords: Macrocyclic (alkene dithiolato)mercury complexes ; Dithiolato complexes ; Stilbene-α,β1-dithiol complexes ; Mercury(II) macrocyclic dithiolato complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of the ligand cis - -S—C(Ph)≡C(Ph)-S-[CH2]n - S - C(Ph)=C(Ph)-S- with n=3 (dianion of 1) with HgCl2 in ethanol produces a yellow linearly trinuclear, μ1-S and μ1-Cl-bridged complex of composition C62H52Cl2Hg3S8 (4), in which the central Hg(II) ion is in a near octahedral arrangement of four Hg—S and two Hg—Cl bonds, whereas the two terminal Hg(II) ions are tetracoordinated with three Hg—S bonds and one Hg—Cl bond in distorted tetrahedral arrangements. The two ligands are bidentate with respect to the terminal and central Hg(II) ions. The corresponding ligand with n=4 (dianion of 2) reacts with HgCl2 to yield a yellow Hg(II) complex of composition C32H28HgS4 (5), in which the ligand is tetradentate and in the trans-syn configuration. The Hg(II) ion in the unit cell of 5 is pentacoordinated, due to symmetric dimerization of two molecules of 2 by two weak coordinate Hg—S bonds of 3.442(2) Å length.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19931260611
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