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  • Articles  (12)
  • Inorganic Chemistry  (9)
  • nanostructures  (2)
  • 1-Oxa-3-azahexatrienes  (1)
  • 1995-1999  (12)
  • 1
    Electronic Resource
    Electronic Resource
    About some Electrophilic Substitution Reactions with [(CF3S)3C+][AsF-6] (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 435-436 
    Details
    ISSN: 0009-2940
    Keywords: Trifluoromethylthio group ; Carbenium ions ; Diphenylmethane ; Dyes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tris(trifluoromethylthio)carbenium hexafluoroarsenate (1) reacts with N,N-dimethylaniline and anisole to form the corresponding diphenylmethanes 2, 3 with the SCF3 group at the methine carbon atom. During the reaction of 1 with benzene, compounds such as C6H5C(SCF3)3 and C6H5SCF3 are formed along with benzophenone, a product of hydrolysis of the diphenylmethane compound.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280417
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  • 2
    Electronic Resource
    Electronic Resource
    Übergangsmetall-Stannyl Komplexe, 10[1]. Molybdocen- und Wolframocen-Derivate mit zwei unterschiedlichen Liganden der 4. Hauptgruppe (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1131-1142 
    Details
    ISSN: 0009-2940
    Keywords: Stannyl complexes ; Plumbyl complexes ; Tungsten complexes ; Molybdenum complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transition-Metal Stannyl Complexes, 10 - Molybdocen and Wolframocen Derivatives with Two Different Main-Group-4 LigandsReactions of Li[Cp2MSnPh3] (M = Mo, W) with CH3I, BuBr, PhCH2Br, PhC(O)Cl or Br(CH2)nBr (n = 4,5) yield Cp2M(R)SnPh3 [R = CH3, Bu, CH2Ph, C(O)Ph, (CH2)nBr], while tBuBr or CH3C(O)Cl give the hydrido complexes Cp2M(H)SnPh3. A silyl stannyl complex is only obtained from Li[Cp2WSnPh3] and Me3SiOSO2CF3, but not with Me3SiCl or from the anionic Mo complex. In contrast, the reactions of chlorostannanes provide the bis(stannyl) complexes Cp2M(SnR′3)SnPh3 or Cp2M(SnR′2Cl)SnPh3. R/Cl exchange at the tin atom is observed when an excess of the chlorostannane is used. Upon reaction of Li[Cp2MSnPh3] with Ph3PbCl only Cp2M(PbPh3)SnPh3 is formed, while a mixture of Cp2M(PbMe3)SnPh3 and Cp2M(PbMe2Cl)SnPh3 is obtained with Me3PbCl due to redistribution reactions. The structures of Cp2W(SnPh3)C(O)Ph, Cp2W(SnPh3)SntBu2Cl and Cp2W(SnPh3)PbMe2Cl were determined by X-ray structure analyses.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961290924
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  • 3
    Electronic Resource
    Electronic Resource
    Preparation and Reactivity of Tris(trifluoromethylselanyl)carbenium [(CF3Se)3C+] and Trifluoromethylsulfanylacetic Acid Derivatives [(CF3S)3-nCXn(O)R]Dedicated to Professor Max Herberhold on the occasion of his 60th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1383-1388 
    Details
    ISSN: 0009-2940
    Keywords: Trifuoromethylselanyl ; Trifluoromethylsulfanyl ; Acetic acid ; Esters ; Halides ; Hexafluoroarsenate ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction pathways for the synthesis of the (CF3E)3C moieties (E = Se, S) are described. [(CF3Se)3C+][AsF6-] was found to be a suitable synthon for the preparation of (CF3Se)3C derivatives. It can be prepared either from (CF3Se)3C derivatives. It can be prepared either from (CF3Se)4C or (CF3Se)3CF and AsF5 in liquid SO2. Direct access to (CF3Se)3CF was realized by the reaction of FCBr3 with Hg(SeCF3)2. Treatment of [(CF3Se)3C+][AsF6-] with potassium halides provided (CF3Se)3CX (X = F, Cl, Br). A different course took the reaction with KI, as CF3SeSeCF3 and (CF3Se)2C=C(SeCF3)2 were formed as main products. Minor amounts of (CF3Se)3CC(SeCF3)3 were formed which could be isolated and unambiguously characterized. Only two routes led to a threefold CF3S-substituted acetic acid ester (CF3S)3CC(O)OR [R = CH3, (CH3)3C]: Metatheses between (CF3S)2CBrC(O)OCH3 and Hg(SCF3)2 and metalation of (CF3S)2CHC(O)OR [R = CH3, (CH3)3C] with NaH followed by reaction with CF3SCl. Other precursors such as (CF3S)2CXC(O)OR′ [X = H, Br; R′ = Me3Si, (n-C4H9)3Sn] and (CF3S)2CBrC(O) Y (Y = Cl, Br) were synthesized but could not be converted to the corresponding (CF3S)3C derivatives. Attempts to hydrolyze (CF3S)3CC(O)OR to (CF3S)3CC(O)OH failed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961291112
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  • 4
    Electronic Resource
    Electronic Resource
    Highly Substituted Cyclams: Stereoselective Synthesis and Coordination Properties (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 521-528 
    Details
    ISSN: 0009-2940
    Keywords: Macrocycles ; Hydrogenation ; Cyclam, binding constant ; N ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report here a new synthetic route to highly-substituted tetraazamacrocycles. Raney nickel hydrogenation of macrocyclic phenylenediamine-acetylacetone condensation products gives cyclams in high yield with complexes all-cis stereoselectivity. The extensive C-substitution of the cyclam 2a changes its ligand properties markedly. The X-ray structure analyses of NiII, CuII, and ZnII complexes of 2a reveals a deviation of the metal ion coordination geometry from the usual square-planar arrangement. This may account for the differences in the redox properties of the NiII and CuII complexes of 2a leads to more positive oxidation and reduction potentials compared to the analogous unsubstituted cyclam complexes. While the binding constant between Zn(ClO4)2 and 2a is lower by a factor of 105 compared to cyclam, the subsequent binding of uridine to the zinc-cyclam complexes in methanol/water is slightly stronger in the case of 2a · Zn(ClO4)2].
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300412
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  • 5
    Electronic Resource
    Electronic Resource
    Mineralization of Gold Nanoparticles in a Block Copolymer Microemulsion (1996)
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1552-1555 
    Details
    ISSN: 0947-6539
    Keywords: block copolymers ; micelles ; mineralization ; nanostructures ; thin films ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Controlled mineralization of gold nanoparticles has been performed in a microemulsion of polystyrene-block-poly(2-vinylpyridine). The starting point was the formation of a thermodynamically stable dispersion of HAuCl4 in inverse micelles of the block copolymer in toluene, which became metastable when the gold was reduced. Kinetic control of the transformation allowed the following stages of the mineralization/coagulation process to be stabilized: 1) one gold particle per micelle, 2) aggregated micelles containing two or three gold particles, and 3) a state in which empty micelles coexist with larger polymer-stabilized gold particles. Distinctive variations in the spectra were observed depending on the particle size and whether two particles had formed a couple with orientation-dependent dipolar interactions.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chem.19960021213
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  • 6
    Electronic Resource
    Electronic Resource
    Unsaturated hetero chains, IVPart III: Ref.. Synthesis, structure, and protonation of 1-oxa-3-azahexatrienes (1995)
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1995 (1995), S. 1015-1025 
    Details
    ISSN: 0947-3440
    Keywords: 1-Oxa-3-azahexatrienes ; 1-Oxa-3-azoniahexatriene Salts ; Protonation ; Calculations, ab initio ; Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Differently substituted 1-oxa-3-azahexatrienes 3 were synthesized either by acylation of N-silyl-1-azabutadienes 1 or by a four-step-one-pot procedure starting from the nitriles 5, involving a Wittig-Horner-Emmons-type olefination as the key step. Both methods allow the isolation of the highly reactive compounds 3. The configuration and conformation of 31 in the crystalline state by X-ray diffraction were determined, indicating an (E) configuration of the C=C bond and a gauche conformation of the C=N—C=O subunit. The reactivity of compounds 3 towards tetrafluoroboric acid was studied. Protonation takes place exclusively at the nitrogen atom leading to the 1-oxa-3-azoniahexatriene salts 10. Quantum-chemical ab initio model calculations for all possible structures of the parent substances C4H5NO 9 and C4H6NO+ 14-16 were performed in order to obtain quantitative data regarding the structural and dynamic behavior of these highly flexible molecules in the gas phase.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jlac.1995199506144
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  • 7
    Electronic Resource
    Electronic Resource
    Die Kristallstrukturen von α- und β-K3OClIn memoriam Professor Wilhelm Klemm (1996)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 622 (1996), S. 153-156 
    Details
    ISSN: 0044-2313
    Keywords: Tripotassium oxide chloride ; preparation ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Crystal Structures of α- and β-K3OClThe orange coloured compound K3OCl has been prepared. It exists in a low temperature modification (α-K3OCl) and a high temperature modification (β-K3OCl). The transition temperature is 364 ± 5 K. The crystal structures were determined by x-ray diffraction. α-K3OCl crystallizes at room temperature in the orthorhombic space group Pbnm (Z = 4) with the cell parameters a = b = 723.9(2) pm and c = 1 027.7(2) pm in the anti-GdFeO3-structure type. The high temperature modification β-K3OCl crystallizes (Z = 1) in the cubic space group Pm3m in the β-Ag3SI-structure type with a = 516.2(2) pm (T = 393 K).
    Notes: Die orangefarbene Verbindung K3OCl wurde dargestellt. Sie tritt in einer Tieftemperaturmodifikation (α-K3OCl) und in einer Hochtemperaturmodifikation (β-K3OCl) auf. Die Umwandlungstemperatur beträgt 364 ± 5 K. Die Kristallstrukturen wurden durch Röntgenstrukturanalyse aufgeklärt. α-K3OCl kristallisiert bei Raumtemperatur in der orthorhombischen Raumgruppe Pbnm (Z = 4) mit den Gitterkonstanten a = b = 723,9(2) pm und c = 1 027,7(2) pm im anti-GdFeO3-Strukturtyp. Die Hochtemperaturmodifikation, β-K3OCl, kristallisiert mit Z = 1 in der kubischen Raumgruppe Pm3m im β-Ag3SI-Strukturtyp mit a = 516,2(2) pm (T = 393 K).
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19966220121
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  • 8
    Electronic Resource
    Electronic Resource
    Darstellung und Charakterisierung von RbLiSe im Rahmen einer Struktursystematik für ternäre Interalkalimetallchalkogenide vom Formeltyp ABXProfessor Hanskarl Müller-Buschbaum zum 65. Geburtstag gewidmet (1996)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 622 (1996), S. 1311-1313 
    Details
    ISSN: 0044-2313
    Keywords: Inter alkali metal chalcogenides ; rubidium lithium selenide ; X-ray ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Crystal Structure of RbLiSeRbLiSe is in the system Rb2Se/Li2Se the only ternary phase without mixed crystals of the binary compounds. The single crystal X-ray investigation of this yellow hygroscopic compound leads to the tetragonal space group P4/nmm (Z = 2) with the lattice constants a = 461.6(1) and c = 748.2(3) pm. Its crystal structure confirms a simple rule of expected structure types for inter alkali metal chalcogenides of the general formula ABX.
    Notes: Im System Rb2Se/Li2Se wurde RbLiSe als einzige Phase gefunden. Mischkristallbildung konnte nicht beobachtet werden. Die gelbe, sehr hygroskopische Verbindung kristallisiert nach Einkristalluntersuchungen tetragonal in der Raumgruppe P4/nmm (Z = 2) mit den Gitterkonstanten a = 461,6(1) und c = 748,2(3) pm. Als Vertreter des anti-PbFCl-Strukturtyps befolgt RbLiSe eine von uns empirisch ermittelte „Regel“ zur Struktursystematik der ternären Interalkalimetallchalkogenide des Formeltyps ABX.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19966220806
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  • 9
    Electronic Resource
    Electronic Resource
    Untersuchungen zur thermischen Zersetzung der Ammoniumyttriumhalogenide III. Ammoniumyttriumbromid, (NH4)3YBr6Professor Wolfgang Jeitschko zum 60. Geburtstag gewidmet (1996)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 622 (1996), S. 1612-1616 
    Details
    ISSN: 0044-2313
    Keywords: Ammonium yttrium bromide ; thermal decomposition ; thermochemical data ; phase transition ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigation on the Thermal Decomposition of Ammonium Yttrium Halides. III. Ammonium Yttrium Bromide, (NH4)3YBr6The decomposition equilibria of NH4Br and (NH4)3YBr6 were determined by total pressure measurements. It was shown by high temperature X-ray patterns and DTA that (NH4)3YBr6 and YBr3 show phase transitions in the measured temperature region. An endothermic transition of YBr3 starts near 300°C and is very slow. By interpretation of the thermal decomposition of (NH4)3YBr6, the enthalpy of formation, and the standard entropy was derived. In the system NH4Br/YBr3 only the described phase (NH4)3YBr6 exists.
    Notes: Durch Gesamtdruckmessungen wurden die Zersetzungsgleichgewichte von NH4Br und (NH4)3YBr6 ermittelt. Hochtemperatur-Röntgenaufnahmen und DTA zeigten, daß bei (NH4)3YBr6 und YBr3 im untersuchten Temperaturbereich Phasenumwandlungen erfolgen. Eine endotherme Umwandlung von YBr3 erfolgt oberhalb von 300°C und verläuft sehr langsam. Die Auswertung der thermischen Zersetzung von (NH4)3YBr6 liefert die Bildungsenthalpie ΔHBo((NH4)3YBr6,f,298) = -402 ± 7 kcal/mol und die Standardentropie So((NH4)3YBr6,f,298) = 134 ± 9 cal/Kmol. Eine weitere komplexe Phase existiert im System NH4Br/YBr3 nicht.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19966220927
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  • 10
    Electronic Resource
    Electronic Resource
    Zum Redoxverhalten von Dithiolenkomplexen des Typs [MIV(S2C2R2)2]0 der Nickel-TriadeProfessor Lothar Beyer zum 60. Geburtstag gewidmet (1997)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 159-168 
    Details
    ISSN: 0044-2313
    Keywords: Ni ; Pd ; Pt Dithiolenes ; Redox Reactions ; EPR ; Electrochemistry ; MO Calculations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Redox-Behavior of [MIV(S2C2R2)2]0 Type Dithiolene Complexes of Ni, Pd, and PtCombined electrochemical and EPR spectroscopic investigations on [M(S2C2R2)2]0 dithiolene chelates containing the metal in the formal oxidation state „+4“ (M = Ni, Pd, Pt; R = CH3, C6H5, p-CH3C6H4 and p-CH3OC6H4) are reported. Spectroelectrochemically the „MIII“ species are easily obtained under reductive conditions. The electrochemical oxidation produces the ligand radical in all cases. Depending on the mode of the electrochemical potential (reduction/oxidation) the redox reaction «MIII» complex ⇌ ligand radical can be switched. The chemical oxidation of the [MIV(S2C2R2)2] complexes with Br2 yielded paramagnetic, formally «MV» containing Ni and Pt species. EHT-MO calculations are used for the explanation of the spin-density distribution in the [MS4] unit for the different oxidation state of the metal.
    Notes: Untersuchungen zum Redoxverhalten von Dithiolenkomplexen des Typs [M(S2C2R2)2]0 mit R = CH3, C6H5, p-CH3C6H4 und p-CH3OC6H4 sowie M = Ni, Pd und Pt in der formalen Oxidationsstufe „+4“ durch die kombinierte Anwendung von Elektrochemie/EPR-Spektroskopie sowie Experimente zur chemischen Oxidation der Verbindungen [MIVL2]0 mit Br2 werden berichtet. „Spektroelektrochemisch“ werden unter reduktiven Bedingungen problemlos die „MIII“-Stufen erhalten; oxidative Bedingungen führten prinzipiell zum Ligandenradikal. Der Redoxprozeß erwies sich als „schaltbar“ zwischen „MIII“-Stufe und Ligandenradikal. Die chemische Oxidation der [MIVL2]0-Komplexe mit Br2 führte zu paramagnetischen, formal „MV“ enthaltenden Verbindungen des Ni und Pt. Mittels EHT-MO-Berechnungen werden Aussagen zur Spindichte-Verteilung in der [MS4]-Einheit getroffen.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19976230127
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