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  • Articles  (1,650)
  • Articles: DFG German National Licenses  (1,650)
  • Chemical Engineering  (730)
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  • 2015-2019
  • 1995-1999  (1,650)
  • 2017
  • 1995  (1,650)
  • Chemistry and Pharmacology  (1,477)
  • Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics  (423)
  • Computer Science  (6)
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  • Articles  (1,650)
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  • 2015-2019
  • 1995-1999  (1,650)
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  • 1
    Electronic Resource
    Electronic Resource
    Chemiluminescence in evaluating thermal oxidative stability of acrylonitrile-butadiene-styrene (ABS) copolymers. III. Emulsion-grade products (1995)
    Springer
    Journal of polymers and the environment 3 (1995), S. 199-203 
    Details
    ISSN: 1572-8900
    Keywords: Chemiluminescence ; oxidation ; stability ; acrylonitrile-butadiene-styrene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The thermal oxidative stability of various formulations based on emulsion-grade ABS was studied by the chemiluminescence technique. Emulsion products were found to be essentially less stable than ionic mass polymerization resins. Among the antioxidants studied, Santonox R is clearly more efficient than Irganox 1076 and Irganox 3114, and its superiority is reflected primarily in improved induction period values. The introduction of Tinuvin 770 and Tinuvin 328 UV stabilizers into emulsion resins does not change the durability of the products. In mixtures where both Irganox 1076 and UV stabilizers are present, a certain antagonistic effect was noted at high UV stabilizer concentrations.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02068674
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  • 2
    Electronic Resource
    Electronic Resource
    The stability of 12-molybdosilicic, 12-tungstosilicic, 12-molybdophosphoric and 12-tungstophosphoric acids in aqueous solution at various pH (1995)
    Springer
    Catalysis letters 34 (1995), S. 237-244 
    Details
    ISSN: 1572-879X
    Keywords: metal-oxygen cluster compounds ; heteropoly acids ; stability ; pH ; aqueous solutions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The stabilities of the solid superacids H3Mo12O40, H3PW12O40, H4SiMo12O40 and H4SiW12O40 in aqueous solution have been measured at various values of pH by use of ion chromatographic analyses. The aforementioned acids are completely decomposed at values of pH, 4.0, 5.2, 7.0 and 11.0, respectively. The stabilities in aqueous solution with respect to pH follow the order H4SiW12O40 〉 H3PW12O40 〉 H4SiMo12O40 〉 H3PMo12O40.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00808338
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  • 3
    Electronic Resource
    Electronic Resource
    Stability of non-Markovian polling systems (1995)
    Springer
    Queueing systems 21 (1995), S. 67-95 
    Details
    ISSN: 1572-9443
    Keywords: Polling systems ; stability ; stationary regime
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science
    Notes: Abstract A stationary regime for polling systems with general ergodic (G/G) arrival processes at each station is constructed. Mutual independence of the arrival processes is not required. It is shown that the stationary workload so constructed is minimal in the stochastic ordering sense. In the model considered the server switches from station to station in a Markovian fashion, and a specific service policy is applied to each queue. Our hypotheses cover the purely gated, thea-limited, the binomial-gated and other policies. As a by-product we obtain sufficient conditions for the stationary regime of aG/G/1/∞ queue with multiple server vacations (see Doshi [11]) to be ergodic.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01158575
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  • 4
    Electronic Resource
    Electronic Resource
    Vibration of rods with a concentrated mass in the presence of non-conservative forces (1995)
    Springer
    Archive of applied mechanics 65 (1995), S. 507-521 
    Details
    ISSN: 1432-0681
    Keywords: rod vibrations ; stability ; tip mass ; non-conservative forces ; non-selfadjoint problems
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Summary Separable and non-selfadjoint boundary-value problems representing the vibration of linearly elastic unidimensional systems are considered. The elastic system is modelled as a continuous distributed-parameter system where singularities in the mass distribution function can be neatly taken into account. Specifically, extending Green's function approach, the free vibration, stability and forced vibration of fixed-free rods with a tip mass and under the action of uniformly distributed non-conservative loads have been investigated analytically.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00789092
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  • 5
    Electronic Resource
    Electronic Resource
    Stability of bars made of linear elastic materials with voids (1995)
    Springer
    Archive of applied mechanics 65 (1995), S. 99-109 
    Details
    ISSN: 1432-0681
    Keywords: Key words Bars ; voids ; viscoelasticity ; stability ; critical load
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Summary  Dynamic stability of an elastic bar with voids is considered. Using the Lyapunov approach some new sufficient stability conditions are obtained and explicit expressions for the critical load are derived.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00787903
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  • 6
    Electronic Resource
    Electronic Resource
    Influence of shear deformation on the buckling of elastically supported beams (1995)
    Springer
    Archive of applied mechanics 65 (1995), S. 133-141 
    Details
    ISSN: 1432-0681
    Keywords: Shear deformation ; elastically supported beams ; axial compression ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Summary The influence of shear deformation on the buckling behavior of a beam supported laterally by a Winkler elastic foundation is studied. A full investigation of the bifurcation points at which, under axial load, the beam becomes critical with respect to one or two simultaneous buckling modes is made. The configurations and stabilities of the equilibrium paths that bifurcate from the critical points are derived. From the results of theoretical analysis, it becomes evident that shear deformation has a considerable effect upon the equilibriums and stabilities of the post-buckling of the beam. The results for the Bernoulli-Euler beam can be obtained as a limiting case for those of the present beam by letting the shear stiffness tend to infinity.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00799294
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  • 7
    Electronic Resource
    Electronic Resource
    Modale Behandlung linearer periodisch zeitvarianter Bewegungsgleichungen (1995)
    Springer
    Archive of applied mechanics 65 (1995), S. 178-193 
    Details
    ISSN: 1432-0681
    Keywords: Periodic motion ; modal treatment ; itrations ; time variance ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Übersicht Lineare, periodisch zeitvariante Bewegungsgleichungen treten im Hubschrauber- und Windturbinenbau auf. Der Getriebebau und die Rotordynamik liefern weitere Beispiele. In diesem Bericht wird ein systematischer Weg zu ihrer Lösung dargestellt. Mit dem Ansatz von Hill wird die homogene Lösung über die Lösung eines Eigenwertproblems gewonnen. Nach Anpassung an die Anfangsbedingungen liefert sie die Fundamentalmatrix des Systems. Ähnlich wie bei zeitinvarianten Systemen, existieren auch bei zeitvarianten Systemen Orthogonalitätsbedingungen, die die Eigenvektoren erfüllen. Die Eigenvektoren selbst sind allerdings zeitabhängig. Benutzt man die Eigenvektoren als Ansatzvektor zur Berechnung der erzwungenen Schwingungen (Transformation mit der zeitvarianten Modalmatrix des Systems), so gelingt es, die Bewegungsgleichungen des Systems in entkoppelte, zeitinvariante zu überführen. Sie lassen sich in bekannter Weise lösen. Dieses Vorgehen wird auf eine moderne Windkraftanlage angewandt. Sie wurde zunächst mit 372 Freiheitsgraden modelliert, die aber auf 18 vor der numerischen Weiterbehandlung kondensiert wurden. Das Stabilitätsverhalten und die Antwortspektren auf stochastische Anregung durch den Wind wurden auf dem oben beschriebenen Weg ermittelt.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00799297
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  • 8
    Electronic Resource
    Electronic Resource
    Modale Behandlung linearer periodisch zeitvarianter Bewegungsgleichungen (1995)
    Springer
    Archive of applied mechanics 65 (1995), S. 178-193 
    Details
    ISSN: 1432-0681
    Keywords: Key words Periodic motion ; modal treatment ; itrations ; time variance ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Übersicht  Lineare, periodisch zeitvariante Bewegungsgleichungen treten im Hubschrauber- und Windturbinenbau auf. Der Getriebebau und die Rotordynamik liefern weitere Beispiele. In diesem Bericht wird ein systematischer Weg zu ihrer Lösung dargestellt. Mit dem Ansatz von Hill wird die homogene Lösung über die Lösung eines Eigenwertproblems gewonnen. Nach Anpassung an die Anfangsbedingungen liefert sie die Fundamentalmatrix des Systems. Ähnlich wie bei zeitinvarianten Systemen, existieren auch bei zeitvarianten Systemen Orthogonalitätsbedingungen, die die Eigenvektoren erfüllen. Die Eigenvektoren selbst sind allerdings zeitabhängig. Benutzt man die Eigenvektoren als Ansatzvektor zur Berechnung der erzwungenen Schwingungen (Transformation mit der zeitvarianten Modalmatrix des Systems), so gelingt es, die Bewegungsgleichungen des Systems in entkoppelte, zeitinvariante zu überführen. Sie lassen sich in bekannter Weise lösen. Dieses Vorgehen wird auf eine moderne Windkraftanlage angewandt. Sie wurde zunächst mit 372 Freiheitsgraden modelliert, die aber auf 18 vor der numerischen Weiterbehandlung kondensiert wurden. Das Stabilitätsverhalten und die Antwortspektren auf stochastische Anregung durch den Wind wurden auf dem oben beschriebenen Weg ermittelt.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00799297
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  • 9
    Electronic Resource
    Electronic Resource
    Influence of shear deformation on the buckling of elastically supported beams (1995)
    Springer
    Archive of applied mechanics 65 (1995), S. 133-141 
    Details
    ISSN: 1432-0681
    Keywords: Key words Shear deformation ; elastically supported beams ; axial compression ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Summary  The influence of shear deformation on the buckling behavior of a beam supported laterally by a Winkler elastic foundation is studied. A full investigation of the bifurcation points at which, under axial load, the beam becomes critical with respect to one or two simultaneous buckling modes is made. The configurations and stabilities of the equilibrium paths that bifurcate from the critical points are derived. From the results of theoretical analysis, it becomes evident that shear deformation has a considerable effect upon the equilibriums and stabilities of the post-buckling of the beam. The results for the Bernoulli-Euler beam can be obtained as a limiting case for those of the present beam by letting the shear stiffness tend to infinity.
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    URL: http://dx.doi.org/10.1007/BF00799294
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  • 10
    Electronic Resource
    Electronic Resource
    Vibration of rods with a concentrated mass in the presence of non-conservative forces (1995)
    Springer
    Archive of applied mechanics 65 (1995), S. 507-521 
    Details
    ISSN: 1432-0681
    Keywords: Key words rod vibrations ; stability ; tip mass ; non-conservative forces ; non-selfadjoint problems
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Summary  Separable and non-selfadjoint boundary-value problems representing the vibration of linearly elastic unidimensional systems are considered. The elastic system is modelled as a continuous distributed-parameter system where singularities in the mass distribution function can be neatly taken into account. Specifically, extending Green’s function approach, the free vibration, stability and forced vibration of fixed-free rods with a tip mass and under the action of uniformly distributed non-conservative loads have been investigated analytically.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00789092
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  • 11
    Electronic Resource
    Electronic Resource
    Stability of bars made of linear elastic materials with voids (1995)
    Springer
    Archive of applied mechanics 65 (1995), S. 99-109 
    Details
    ISSN: 1432-0681
    Keywords: Bars ; voids ; viscoelasticity ; stability ; critical load
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Summary Dynamic stability of an elastic bar with voids is considered. Using the Lyapunov approach some new sufficient stability conditions are obtained and explicit expressions for the critical load are derived.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00787903
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  • 12
    Electronic Resource
    Electronic Resource
    A survey on stability of chemical species in solution during storage: the BCR experience (1995)
    Springer
    Microchimica acta 118 (1995), S. 131-141 
    Details
    ISSN: 1436-5073
    Keywords: stability ; chemical species ; solutions ; calibration ; interlaboratory studies ; measurement and testing programme
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The stability of chemical species in solution during storage is one of the critical aspect that has to be carefully studied e.g. for calibration purposes or prior to the organization of interlaboratory studies using synthetic solutions. The Measurements and Testing Programme (formerly BCR) is currently undertaking projects to improve the quality of speciation analysis for a variety of species (e.g. As, Hg, Sn, Pb, Cr). In all the cases the stability of these species was carefully studied in the solutions provided to the participants. This paper gives an overview of some of the results obtained in different BCR-projects on speciation analysis.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01242236
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  • 13
    Electronic Resource
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    The shakedown load boundary of an elastic-perfectly plastic structure (1995)
    Springer
    Meccanica 30 (1995), S. 155-174 
    Details
    ISSN: 1572-9648
    Keywords: Shakedown theory ; Cyclic loads ; Structural plasticity ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario Nell'ipotesi di piccoli spostamenti e di plasticità perfetta, si studiano le proprietà geometrico-meccaniche della frontiera del dominio dei carichi di adattamento. Si mostra come, nello spazio dei carichi, la suddetta frontiera giuoca il ruolo di superficie di plasticizzazione ed un particolare vettore di deformazione plastica accumulata—che caratterizza il meccanismo di non adattamento—segue la legge della normalità, mentre una forma specifica del teorema del massimo lavoro plastico costituisce un valido strumento per la valutazione del carico limite corrispondente ad un dato meccanismo di non adattamento. Si forniscono altresì le equazioni che governano lo stato della struttura al limite di adattamento, mostrando la capacità del relativo meccanismo di collasso a rappresentare la risposta a lungo termine della struttura a dei carichi periodici inviluppanti il dominio dei carichi con una intensità un poco al di sopra del limite di adattamento.
    Notes: Abstract In the hypothesis of small displacements and combined time-variable/steady loads, the geometrical-mechanical properties of the shakedown load boundary are investigated. It is shown that, in the load space, the shakedown load boundary plays the role of yield surface, and that a certain plastic strain accumulation vector—characterizing some impending inadaptation collapse mechanism—obeys the normality rule, whereas a specific form of the maximum plastic work theorem constitutes an effective tool for the evaluation of the shakedown limit load corresponding to a specified inadaptation collapse mode. The equations governing the state of the structure at the shakedown limit are provided and the related collapse mechanism is shown to specify the shape of the steady-state response of the structure to a periodic load enveloping the load domain with an intensity slightly above the shakedown limit.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00990454
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  • 14
    Electronic Resource
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    Mohr's arbelos (1995)
    Springer
    Meccanica 30 (1995), S. 417-424 
    Details
    ISSN: 1572-9648
    Keywords: Mohr's circles ; Stress representation ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario Si ottiene la classica rappresentazione di O. Mohr dello stato tensionale con i metodi del calcolo di estremi condizionati.
    Notes: Abstract The classical representation of the stress state due to O. Mohr is obtained by using the calculus of constrained extrema.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00993424
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  • 15
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    Some examples of electron microscopy studies of microstructures and phase transitions in solids (1995)
    Springer
    Meccanica 30 (1995), S. 433-438 
    Details
    ISSN: 1572-9648
    Keywords: Electron microscopy ; Microstructures ; Phase transitions ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario Si presentano i risultati di alcuni studi fatti attraverso la microscopia elettronica sulle microstrutture relative a transizioni di fase in una varietà di materiali. I casi comprendono leghe binarie e ternarie, superconduttori TC e materiali C60 e C70; le transizioni esaminate sono diffusionali, displacive o di entrambi i tipi.
    Notes: Abstract In this contribution the results of some electron microscopy studies on microstructures related with phase transitions in a variety of materials will be presented. The materials include binary and ternary alloys, high TC superconductors as well as C60 and C70 fullerenes, while the transitions can be diffusional, displacive or both.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01557075
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  • 16
    Electronic Resource
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    Nonlinear dynamics and stability of microstructures in a lattice model for ferroelastic materials (1995)
    Springer
    Meccanica 30 (1995), S. 449-458 
    Details
    ISSN: 1572-9648
    Keywords: Lattice ; Nonlinear waves ; Ferroelasticity ; Phase transformations ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario Si propone un modello reticolare che può descrivere complessi arrangiamenti fatti di domini elastici ed interfacce. Sulla base di un modello bidimensionale in cui sono presenti interazioni contrastanti e nonlineari si esamina la dinamica della formazione di microstrutture. L'accento è posto sui meccani'smi di instabilità che determinano bande di deformazione localizzata. Si studia l'influenza delle forze applicate e degli effetti dissipativi sulla dinamica di due bande perpendicolari e si interpretano i risultati come un microtwinning in leghe cristalline. Si verificano le congetture fisiche per mezzo di simulazioni numeriche del modello microscopico.
    Notes: Abstract With the view of understanding how precise macroscopic properties of a material emerge from the underlying physics of homogeneous microstructures, a lattice model which can describe complex non-linear patterns made of elastic domains and interfaces is proposed. On the basis of a two-dimensional lattice model involving non-linear and competing interactions the dynamics of microstructure formation is examined. The emphasis is placed especially on an instability mechanism of a strain band producing localized domains. The influence of applied forces and dissipative effects on the dynamics of two perpendicular strain bands is studied. The results are interpreted as a microtwinning in crystalline alloys. The physical conjectures are checked by means of numerical simulations performed directly on the microscopic system.
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    URL: http://dx.doi.org/10.1007/BF01557077
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  • 17
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    Martensitic transformation and phonon localization in Ni-Al alloys by atomistic simulations (1995)
    Springer
    Meccanica 30 (1995), S. 439-448 
    Details
    ISSN: 1572-9648
    Keywords: Martensitic transformation ; Atomistic simulation ; Phonon localization ; Phase transitions ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario L'articolo discute un modello ‘Embedded Atom’ per l'energia potenziale di leghe Ni-Al. Il potenziale viene utilizzato in uno studio di Dinamica Molecolare e nell'approssimazione Quasi Armonica della Transformazione Martensitica (MT) che ha luogo in Ni x Al1−x per 0.61〈x〈0.64 a una temperatutaT M compresa tra ~ 0 K perx=0.61 e ~ 400 K perx=0.64. La temperature di transizione è determinata in funzione della composizione e della pressione. I risultati dimostrano la validità del potenziale nel riprodurre le proprietà note della lega. Il modello viene utilizzato per studiare la dinamica microscopica alla base della trasformazione. Lo studio mostra che nella austenite il disordine chimico legato alla non-stechiometria induce bande di fononi localizzati che si delocalizzano in modo discontinue allaMT. Viene mostrato che i modi localizzati sono associati a regioni rieche di Ni ed individuano siti di incipiente instabilità reticolare. Tali siti forniscono centri preferenziali per la nucleazione.
    Notes: Abstract We discuss an atomistic model for the potential energy of Ni-Al alloys based on the Embedded Atom Method. The potential is applied in a Molecular Dynamics and Quasi Harmonic investigation of the Martensitic Transformation (MT) that occurs in Ni x Al1− x for compositions 0.61〈x〈0.64 at a temperatureT M ranging from ~ 0 K atx=0.61 to ~ 400 K atx=0.64. We determine the transition temperature as a function of composition and pressure and we show that our potential reliably reproduces the known properties of the alloy. We exploit the model to investigate the microscopic dynamical properties underlying the transition. Our computation shows that in the austenite the compositional disorder induces several bands of localized phonons, that discontinuously de-localize at the MT. We show that specific localized modes associated with Ni-rich clusters identify regions of incipient lattice instability, and provide favourable sites for the nucleation.
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    URL: http://dx.doi.org/10.1007/BF01557076
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  • 18
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    Internal loops in pseudoelastic behaviour of Ti-Ni shape memory alloys: Experiment and modelling (1995)
    Springer
    Meccanica 30 (1995), S. 459-466 
    Details
    ISSN: 1572-9648
    Keywords: Shape memory alloys ; Titanium-nickel ; Pseudoelasticity ; Martensitic transformation ; Phase transitions ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario Per leghe Ti-Ni con memoria di forma vengono analizzati i cicli di isteresi isotermici tensione-deformazione prodotti da una incompleta trasformazione martensitica. Gli esperimenti mostrano l'esistenza di due distinte linee di snervamento per la transizione di fase, una verso la trasformazione austenite→martensite (A→M), l'altra per la trasformazione inversa M→A. Il comportamento a trazione di un singolo cristallo con una sola linea di snervamento (A↔M) [1], può essere considerato un caso ideale. L'estensione ad un modello termodinamico pseudo-elastico [2] consente di analizzare queste due linee di snervamento.
    Notes: Abstract The stress-strain isothermal hysteresis loops due to the incomplete martensitic transformation are analysed for Ti-Ni shape memory alloys. Experiments show the existence of two distinct yield lines for phase transition; one for the forward transformation austenite→martensite (A→M), the other for the reverse transformation M→A. The tensile behaviour of single crystals with only one yield line (A↔M) [1] can be considered as an ‘ideal’ case. An extension of a thermodynamic model for pseudoelasticity [2] allows these two yield lines to be taken into account.
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    URL: http://dx.doi.org/10.1007/BF01557078
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  • 19
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    Beyond young measures (1995)
    Springer
    Meccanica 30 (1995), S. 505-526 
    Details
    ISSN: 1572-9648
    Keywords: Young measures ; H-measures ; Microstructures ; Phase transitions ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario Si discutono le misure di Young e le loro limitazioni. Alcune relazioni che intercorrono tra le misure di Young e le H-misure sono descritte ed utilizzate nello studio di un esempio tratto dalla meccanica di mezzi micromagnetici. Si evidenzia in particolare la necessità di migliorare la teoria delle H-misure e di altre misure semi-classiche.
    Notes: Abstract Young measures and their limitations are discussed. Some relations between Young measures and H-measures are described and used to analyze an example from micromagnetics. The need to improve H-measures and semi-classical measures is stressed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01557082
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    The step-wise martensite to austenite reversible transformation (1995)
    Springer
    Meccanica 30 (1995), S. 495-503 
    Details
    ISSN: 1572-9648
    Keywords: Martensitic transformation ; Shape memory alloys ; Transformation kinetics ; Phase transformations ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario Con l'acronimo di SMART (step-wise martensite to austenite reversible transformation) si indica una trasformazione martensitica termoelastica in cui la cinetica di trasformazione risulta modificata dall'esecuzione di un'appropriata procedura di ciclaggio termico parziale (procedura ICH — Incomplete Cycle on Heating) nell'intervallo di temperatura in cui ha luogo la trasformazione martensitica inversa. Vengono qui presentati i risultati sperimentali relativi sia alla SMART sia agli effetti indotti dalla procedure ICH e responsabili delle modifiche della cinetica di trasformazione. Vengono inoltre discusse le ipotesi sino ad ora avanzate per spiegare i risultati sperimentali.
    Notes: Abstract The step-wise martensite to austenite reversible transformation (SMART) in shape memory alloys (SMA) is a martensitic thermoelastic transformation where a step-wise kinetics is induced by a partial cycling procedure within the hysteresis cycle (incomplete cycle on heating (ICH) procedure). The ICH procedure has been proved effective in inducing a reversible microstructural modification of the martensitic phase. Results till now obtained both on the SMART behaviour and on the effects of the ICH procedure are reviewed here: the hypotheses advanced till now are discussed to explain experimental evidences.
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    A Classification of thermodynamical potentials for two-variable transition systems (1995)
    Springer
    Meccanica 30 (1995), S. 475-494 
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    ISSN: 1572-9648
    Keywords: Thermodynamical potential ; Nonconvex energy ; Phase transitions ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario II lavoro suggerisce una possibile classificazione dei potenziali termodinamici per sistemi con due variabili di stato soggetti a transizioni di fase e, per ogni classe individuata, mostra le caratteristiche e i diagrammi tipici dell'energia interna, l'entalpia, le energie libere di Helmholtz e Gibbs. Potenziali termodinamici a più valori appaiono essere la regola più che l'eccezione. Nell'ambito della classificazione trovata sono studiati vari esempi noti, come il gas di van der Waals e il modello di Landau-Devonshire.
    Notes: Abstract We suggest here a possible classification of the thermodynamical potentials for phase transition systems with two state variables. Within each of the single-typed classes, the characters and typical diagrams of the internal energy, enthalpy, Helmholtz and Gibbs free energy are shown. Multivalued potentials appear to be the rules rather than the exceptions. Several known examples of phase transitions, e.g. van der Waals gas, Landau-Devonshire model, are studied within the framework of the present classification.
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    The influence of surface energy on stress-free microstructures in shape memory alloys (1995)
    Springer
    Meccanica 30 (1995), S. 527-539 
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    ISSN: 1572-9648
    Keywords: Microstructures ; Shape memory alloys ; Variational methods ; Surface energy ; Phase transformations ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario Certe leghe come quelle di In-Tl, Ni-Ti, Ag-Cd o Cu-Al-Ni mostrano proprietà meccaniche notevoli quali la memoria di forma o la pseudoelasticità. Questo comportamento è determinato da una trasformazione di fase solido-solido che conduce a complicati arrangiamenti a livelo microscopico. In studi recenti tali microstrutture sono state analizzate attraverso la minimizzazione dell'energia elastica. Noi discutiamo l'influenza di termini addizionali di energia superficiale sull'esistenza di microstrutture in uno stato naturale sia in un contesto lineare che non lineare.
    Notes: Abstract Certain alloys such as In-Tl, Ni-Ti, Ag-Cd or Cu-Al-Ni display remarkable mechanical properties such as the shape memory effect or pseudo-elasticity. This behaviour is related to a solid-solid phase transformation which leads to a complicated microscopic arrangement of different phases. In recent studies such microstructures have been analyzed by the minimization of elastic energy. We discuss the influence of additional surface energy terms on the existence of stress-free microstructures both in the nonlinear and a geometrically linear setting.
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    Phase transitions and hysteresis in nonlocal and order-parameter models (1995)
    Springer
    Meccanica 30 (1995), S. 541-565 
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    ISSN: 1572-9648
    Keywords: Phase transitions ; Hysteresis ; Order-parameter ; Nonlocal equations ; Phase transformations ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario Il lavoro descrive due tipi di regolarizzazione del problema quasistatico per un potenziale con due minimi in una dimensione. Un modello evidenzia caratteri di non località spaziale, mentre l'altro conduce ad una teoria con parametro d'ordine. Si derivano alcuni risultati di esistenza e regolarità e si presentano alcuni studi numerici che mostrano l'isteresi e il moto delle frontiere tra le fasi.
    Notes: Abstract The paper describes two types of regularization to the basic quasistatic double-well potential problem in one space dimension. One model features a spatially nonlocal term while the other incorporates the use of an order parameter. Some basic existence and regularity results for these modified models are derived and some numerical calculations that show hysteresis and motion of phase boundaries are presented.
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    A one-dimensional model for incoherent phase changes (1995)
    Springer
    Meccanica 30 (1995), S. 567-575 
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    ISSN: 1572-9648
    Keywords: Incoherent phase transitions ; Vacancy diffusion in solids ; Phase transitions ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario In questo lavoro viene presentato un adattamento del modello di transizione di fase incoerente sviluppato da Gurtin e Cermelli in [3]. Una transizione incoerente è sempre associata alla produzione di un qualche tipo di difetto all'interfaccia: consideriamo qui un modello semplificato di continuo unidimensionale, in modo da poter studiare l'effetto dei difetti di volume (lacune) sull'evoluzione del sistema.
    Notes: Abstract We present here a simplified version of the model of incoherent solid-solid transitions with mass diffusion developed by Gurtin and Cermelli in [3]. An incoherent phase change is always associated with some kind of defect production at the interface: we consider here a one-dimensional continuum, so that the resulting equations allow study to be made of the influence of volume (vacancy) production on the evolution of the system.
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    Hysteresis and imperfection sensitivity in small ferromagnetic particles (1995)
    Springer
    Meccanica 30 (1995), S. 591-603 
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    ISSN: 1572-9648
    Keywords: Imperfection sensitivity ; Hysteresis ; Local minimizers ; Variational methods ; Phase transformations ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario Si deducono i classici risultati di Stoner e Wohlfarth dalla teoria del micromagnetismo, e si dimostra la loro validità per la previsione di cicli di isteresi magnetica anche per particelle di forma non ellissoidale. Viene proposta, quale possibile spiegazione della notevole ampiezza dei cicli di isteresi caratteristici di particelle di piccole dimensioni, l'indifferenza alla presenza di rugosità superficiale.
    Notes: Abstract The classical results of Stoner and Wohlfarth for the prediction of hysteresis loops in small ferromagnetic particles are extended to specimens of non-ellipsoidal shape, and shown to be a consequence of micromagnetics. The insensitivity to surface roughness is proposed as a possible explanation of the high coercivity behavior of small particles.
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    Smectic liquid crystals as continua with latent microstructure (1995)
    Springer
    Meccanica 30 (1995), S. 621-627 
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    ISSN: 1572-9648
    Keywords: Liquid crystals ; Smectics ; Nematics ; Continuum models ; Phase transitions ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario I cristalli liquidi smettici sono quasi-solidi che possiedono una microstruttura sia di tipo materiale che locale (la microstruttura nematica e le lamelle, rispettivamente). Essi esibiscono anche transizioni di fase: smettici B a smettici A, a nematici, a liquidi isotropi. Il loro studio, sebbene speciale, potrebbe evidenziare vantaggi generali e difetti di vari tipi di modelli matematici. Qui, nel provare la proprietà annunciata nel titolo, si prepara il lavoro di base per il modello continue.
    Notes: Abstract Smectic liquid crystals are quasi solids, which possess microstructure both of the material and local type (the nematic mictrostructure and the lamellae, respectively). They also exhibit phase transitions: from smectic B to smectic A, to nematic, to isotrtopic liquid (see [1], Ch. 7). Their study, though special, might show up general advantages and drawbacks of different types of mathematical models. Here, while intent on proving the property announced in the title, we set forth the groundwork for the continuum model (see, in a more specific and concrete mode [2]).
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    Inertial and self interactions in structured continua: Liquid crystals and magnetostrictive solids (1995)
    Springer
    Meccanica 30 (1995), S. 629-640 
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    ISSN: 1572-9648
    Keywords: Liquid crystals ; Magnetostrictive solids ; Continua with microstructure ; Phase transformations ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario Si discutono equazioni di evoluzione per cristalli liquidi e per solidi magnetostrittivi nell'ambito di una teoria dei continui con microstruttura che contempla la possibilità sia di autointerazioni meccaniche che di termini inerziali non standard.
    Notes: Abstract Evolution equations for liquid crystals and for magnetostrictive solids are discussed within the framework of a theory of continua with microstructure that allows for mechanical self-interactions and non-standard inertial terms.
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    The dynamics of configurational forces at phase-transition fronts (1995)
    Springer
    Meccanica 30 (1995), S. 605-619 
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    ISSN: 1572-9648
    Keywords: Thermoelasticity ; Dynamics ; Configurational forces ; Phase transitions ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario Si osserva preliminarmente che, per alcune trasformazioni di fase nei solidi, la più naturale descrizione del fenomeno nell'ambito del continuo sembra essere quella basata sul moto inverse in dinamica, o sulla deformazione inversa in statica. In tale quadro, la nozione di ‘coerenza di fase’, suggerita dalla congruenza geometricocinematica tra due distinti reticoli cristallini a contatto, trova la sua espressione più significativa nella condizione di continuità degli ‘spostamenti di siti’ nel riferimento cristalline. Sulla base di argomentazioni svolte in precedenti lavori dagli autori per il caso dinamico e da M. Epstein per il caso statico e termostatico, si presuppone valida un'equazione di bilancio ‘materiale’: quella dellapseudo-quantità di moto. Si richiede che tale bilancio sia soddisfatto attraverso una superficie di contatto tra le due fasi. Tale superficie o fronte, avanzando, determina la trasformazione del materiale da una fase nell'altra. Il fronte è suppostoomotermo ed il materiale termoelastico in ciascuna delle due fasi. Un ruolo chiave è svolto dal tensore degli sforzi materiali di Eshelby. Infatti, la potenza sviluppata dalle forze di disomogeneità attraverso il fronte che avanza è unicamente determinata dalla discontinuità del tensore di Eshelby lungo la normale al fronte. Inoltre, l'espressione che detta potenza assume permette di evidenziare una quantità scalare che proponiamo di denominareforza configurazionale di Hugoniot-Gibbs per le analogie che essa suggerisce. Si sviluppa infine una trattazione parallela sulla base di una formulazione termodinamica classica del continuo. Un confronto dei risultati permette di Stabilire che la potenza sviluppata dalla forza configurazionale viene dissipata mentre il fronte avanza.
    Notes: Abstract First we recognize that the coherence of certain phase transformations in solids is most vividly expressed using the material manifold and within the kinematic continuum description based on the so-calledinverse motion. In this fully dynamical framework the equation of interest is theun-balance of pseudomomentum for thermoelastic conductors. On computing the power developed by the accompanying surface source of quasi-inhomogeneities at the phase-transition front, we show that this relates directly to the normal jump of the Eshelby stress — devoid of any kinetic energy, but computed from the free energy — a scalar quantity which may be referred to as theHugoniot-Gibbs configurational force at the front. The thermodynamic analysis also establishes that this power is dissipated as the material progresses at the front that ishomothermal. The jump relation including this dissipation is that associated with the heat propagation equation valid at regular points. In all, this approach is based on the theory of material uniformity and inhomogeneities as developed in recent years by M. Epstein and the authors. All reasonings are made in full dynamics, for finite strains, and any anisotropy in three dimensions.
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    Finite-scale microstructures and metastability in one-dimensional elasticity (1995)
    Springer
    Meccanica 30 (1995), S. 577-589 
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    ISSN: 1572-9648
    Keywords: Microstructures ; Interface energy ; Non convex variational problems ; Phase transitions ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario Il lavoro riguarda la non unicità messa in luce da J.L. Ericksen nella sua analisi dell'equilibrio di barre elastiche con energia non convessa. Seguendo le linee di precedenti lavori, per investigare questa degenerazione si ricorre ad una regolarizzazione del problema e si dà un esplicito quadro di riferimento per lo studio della ricca varietà delle microstrutture di scala finita e della loro stabilità. Si chiarisce in particolare il ruolo dell'energia di interfaccia nella creazione di microstrutture di scala finita considerando l'effetto combinato di termini inibitori e favorevoli all'insorgere di oscillazioni nel funzionale energia.
    Notes: Abstract This paper addresses the non-uniqueness pointed out by Ericksen in his classical analysis of the equilibrium of a one-dimensional elastic bar with non-convex energy [1]. Following some previous work in this area, we suitably regularize the problem in order to investigate this degenerancy. Our approach gives an explicit framework for the the study of the rich variety offinite-scale equilibrium microstructures for the bar in a hard loading device, and their stability properties. In this way we clarify the role of interfacial energy in creating finitescale microstructures, by considering the combined effect of the oscillation-inducing and oscillation-inhibiting terms in the energy functional.
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    A two-dimensional polycrystal model in a ‘deep’ space representation (1995)
    Springer
    Meccanica 30 (1995), S. 641-663 
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    ISSN: 1572-9648
    Keywords: Polycrystal ; Rate-independent plasticity ; Texture ; Phase transformations ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario Proponiamo un modello che collega la deformazione macroscopica all'evoluzione della tessitura cristallina. Questo modello si rifà a variabili microstrutturali per descriverelo stato ‘profondo’ del policristallo; le velocità di tali variabili entrano nell'espressione della potenza virtuale in uno con le microtensioni ad esse associate. Termini supplementari appropriati appaiono inoltre nelle equazioni di bilancio dell'energia e dell'entropia. Viene utilizzato il criterio di Schmid per i singoli sistemi di scivolamento per scrivere una delle equazioni costitutive necessarie. Viene quindi introdotto un assunto simile al criterio di Taylor-Bishop-Hill per i policristalli per mettere in relazione il gradiente di velocità e la velocità di rotazione del reticolo cristallino via la combinazione di scivolamenti attiva. Il modello viene applicato ad un esempio mostrando buon accordo con un policristallo piano alla Taylor per una scelta particolare dei legami costitutivi delle microtensioni.
    Notes: Abstract We propose a model which links macroscopic deformations with changes in crystalline texture. The model calls upon microstructural variables to describe the state of the polycrystal; their time-rates, together with the corresponding microstresses, enter the expression of virtual power. Appropriate supplementary terms also appear in the equations of balance of energy and entropy. Schmid's law for single slip systems is invoked to provide one of the additional constitutive equations. A constitutive statement similar to the Taylor-Bishop-Hill criterion for polycrystals is introduced to relate the velocity gradient and the lattice spin via the active spin combination. The model is applied to an example agreeing with a Taylor planar polycrystal for a particular choice of constitutive laws for the microstresses.
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    A new form of the coherency energy in pseudoelasticity (1995)
    Springer
    Meccanica 30 (1995), S. 467-474 
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    ISSN: 1572-9648
    Keywords: Pseudoelasticity ; Coherency ; Hysteresis ; Phase transitions ; Solid mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Sommario Nella modellazione delle trasformazioni martensitiche gioca un ruolo essenziale la rappresentazione dell'energia di coerenza tra le fasi. Seguendo una recente proposta di Rogers, in questo lavoro si investiga una forma di tale energia che dipende dalla deformazione di trasformazione.
    Notes: Abstract In some previous papers [1], [2] pseudoelasticity in tensile experiments has been treated thermodynamically under the assumption that the relevant constitutive ingredients are (i) a non-convex free energy; (ii) coherency between the austenitic and martensitic phase. The form of the coherency energy was assumed to be proportional to the product of phase fractions of the two phases. Recently Rogers [3] has proposed a slight variation of this ansatz: The factor of proportionality should depend on the transformation strain. This new form of coherence energy is investigated in this paper. An attractive feature of this new assumption is that the strains of the coexisting phases in equilibrium remain unchanged as the transformation proceeds. The entropy production inside the pseudoelastic hysteresis is explored for various straight (P, d)-curves.
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    Technical note: Bias and the quantification of stability (1995)
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    Machine learning 20 (1995), S. 23-33 
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    ISSN: 0885-6125
    Keywords: stability ; bias ; accuracy ; repeatability ; agreement ; similarity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science
    Notes: Abstract Research on bias in machine learning algorithms has generally been concerned with the impact of bias on predictive accuracy. We believe that there are other factors that should also play a role in the evaluation of bias. One such factor is the stability of the algorithm; in other words, the repeatability of the results. If we obtain two sets of data from the same phenomenon, with the same underlying probability distribution, then we would like our learning algorithm to induce approximately the same concepts from both sets of data. This paper introduces a method for quantifying stability, based on a measure of the agreement between concepts. We also discuss the relationships among stability, predictive accuracy, and bias.
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    Technical Note: Bias and the Quantification of Stability (1995)
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    Machine learning 20 (1995), S. 23-33 
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    ISSN: 0885-6125
    Keywords: stability ; bias ; accuracy ; repeatability ; agreement ; similarity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science
    Notes: Abstract Research on bias in machine learning algorithms has generally been concerned with the impact of bias on predictive accuracy. We believe that there are other factors that should also play a role in the evaluation of bias. One such factor is the stability of the algorithm; in other words, the repeatability of the results. If we obtain two sets of data from the same phenomenon, with the same underlying probability distribution, then we would like our learning algorithm to induce approximately the same concepts from both sets of data. This paper introduces a method for quantifying stability, based on a measure of the agreement between concepts. We also discuss the relationships among stability, predictive accuracy, and bias.
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    The relationship between physical property and function of highly activated mutants of thermolysin (1995)
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    Molecular engineering 5 (1995), S. 245-253 
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    ISSN: 1572-8951
    Keywords: Protein engineering ; thermolysin ; activity ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermolysin mutants having a variety of amino acid at the 119th position are designed by considering electrostatic field effect upon the active area. The most activated mutant has five times higher hydrolytic activity than the wild type. Negative correlation between the activity and the thermal stability is observed. A combined effect of the flexibility of the substrate binding site and the negative electrostatic field around the site is suggested as a key to enhance the activity.
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    Stability analysis of a general toeplitz systems solver (1995)
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    Numerical algorithms 10 (1995), S. 225-244 
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    ISSN: 1572-9265
    Keywords: Cholesky factorization error analysis ; Hankel matrix ; least squares ; normal equations ; orthogonal factorization ; QR factorization ; semi-normal equations ; stability ; Toeplitz matrix ; weak stability ; Primary 65F25 ; Secondary 47B35 ; 65F05 ; 65F30 ; 65Y05 ; 65Y10
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science , Mathematics
    Notes: Abstract We show that a fast algorithm for theQR factorization of a Toeplitz or Hankel matrixA is weakly stable in the sense thatR T R is close toA T A. Thus, when the algorithm is used to solve the semi-normal equationsR TRx=AT b, we obtain a weakly stable method for the solution of a nonsingular Toeplitz or Hankel linear systemAx=b. The algorithm also applies to the solution of the full-rank Toeplitz or Hankel least squares problem min ||Ax-b||2.
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    Multistep methods for differential algebraic equations (1995)
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    Numerical algorithms 10 (1995), S. 245-260 
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    ISSN: 1572-9265
    Keywords: Multistep methods ; differential-algebraic equations ; stability ; existence and uniqueness ; convergence of iterative method ; 65L06 ; 65L20 ; 65N22
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science , Mathematics
    Notes: Abstract Multistep methods for the differential/algebraic equations (DAEs) in the form of $$F_1 (x) = 0, F_2 (x,x',z) = 0$$ are presented, whereF 1 maps from ℝ n to ℝ ′ ,F 2 from ℝ n x ℝ n x ℝ m to ℝ s andr〈n≤r+s=n+m. By employing the deviations of the available existence theories, a new form of the multistep method for solutions of (1) is developed. Furthermore, it is shown that this method has no typical instabilities such as those that may occur in the application of multistep method to DAEs in the traditional manner. A proof of the solvability of the multistep system is provided, and an iterative method is developed for solving these nonlinear algebraic equations. Moreover, a proof of the convergence of this iterative method is presented.
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    A study of the construction of lyapunov function for a class of fourth order nonlinear systems (1995)
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    Applied mathematics and mechanics 16 (1995), S. 195-202 
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    ISSN: 1573-2754
    Keywords: nonlinear ; stability ; Lyapunov function
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Mathematics , Physics
    Notes: Abstract In the paper Lyapumov function for a fourth order linear system is given and stability of the trivial solutions to a class of fourth order nonlinear systems is studied.
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    Stability for the equilibrium state of Chaplygin's systéms (1995)
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    Applied mathematics and mechanics 16 (1995), S. 635-642 
    Details
    ISSN: 1573-2754
    Keywords: analytic mechanics ; nonholonomic system ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Mathematics , Physics
    Notes: Abstract The stability for the equilibrium states of Chaplygin's systems is considered. The equations of motion of Chaplygin's systems and the existence conditions of their equilibrium states are given. Some criteria of stability for the equilibrium. states of Chaplygin's systems are obtained. Two examples are finally given.
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    Stability of traffic patterns in broadband networks (1995)
    Springer
    Journal of network and systems management 3 (1995), S. 371-380 
    Details
    ISSN: 1573-7705
    Keywords: Telephone traffic ; network management ; control theory ; dynamic flows ; stability ; routing algorithms ; broadband networks ; simulation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science
    Notes: Abstract The control of telephony traffic is the task of network management and routing algorithms. In this paper, a study of two trunk groups carrying telephony traffic is used to show that instabilities can arise if there is a delay in getting feedback information for a network controller. The network controller seeks to balance the traffic in the two trunk groups, which may represent two paths from a source to a destination. An analysis shows how factors such as holding time, controller gain and feedback delay influence stability. Simulation of a two service case is also carried out to show that the same instabilities can arise.
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    URL: http://dx.doi.org/10.1007/BF02139530
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    A New Strategy for Enhancing the Stability of Lyophilized Protein: The Effect of the Reconstitution Medium on Keratinocyte Growth Factor (1995)
    Springer
    Pharmaceutical research 12 (1995), S. 1447-1452 
    Details
    ISSN: 1573-904X
    Keywords: proteins ; aggregation ; reconstitution ; lyophilization ; additives ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. Protein stabilization during lyophilization has previously focused on optimization of the formulation as well as the freezing and dehydration process parameters. However, the effect of the reconstitution medium has been largely neglected. We have investigated its effect on aggregate formation using recombinant keratinocyte growth factor (KGF). Methods. The protein was lyophilized under suboptimal conditions to induce aggregation and precipitation upon reconstitution with water. A series of additives were examined by UV spectrophotometry and size exclusion chromatography (SEC-HPLC) for their effects on decreasing the degree of KGF aggregation and precipitation by the increase in recovery of soluble monomer. Results. Several additives resulted in a significant reduction of aggregation, including sulfated polysaccharides, surfactants, polyphosphates, and amino acids. A similar effect was achieved by adjusting the ionic strength of the reconstitution medium. SEC-HPLC indicated that the amount of soluble monomer was also increased by these additives suggesting that the recovery of the soluble protein correlates with the native, monomeric protein. Conclusions. These results suggest that optimization of reconstitution conditions will be a useful methodology for increasing the recovery of soluble, active proteins and that for KGF, the recovery of the soluble protein correlates with the native, monomeric form.
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    URL: http://dx.doi.org/10.1023/A:1016219000963
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    Isothermal and Nonisothermal Decomposition of Famotidine in Aqueous Solution (1995)
    Springer
    Pharmaceutical research 12 (1995), S. 599-604 
    Details
    ISSN: 1573-904X
    Keywords: famotidine ; degradation ; isothermal ; nonisothermal ; kinetics ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of hydrolysis of famotidine in aqueous solution was studied by isothermal and nonisothermal method over the pH range of 1.71 to 10.0. Nonisothermal kinetics was studied with the purpose of determining its use in the establishment of the expiration date of pharmaceutical preparations, particularly drugs in solutions and for assessment of stability characteristics of pharmaceutical formulations during the development stage. A comparison of isothermal (55, 70 and 85°C) and nonisothermal kinetics was performed. Aqueous solutions of famotidine were buffered at pH 1.71, 2.24, 2.66, 4.0, 8.5, 9.0 and 10.0 were used. In the nonisothermal studies, the temperature rate of the reaction was continuously varied throughout the experiment. The energies of activation were found to be in close agreement for isothermal and nonisothermal studies, indicating that nonisothermal studies may save considerable amount of time in the early stages of drug development and stability testing. Logk-pH profiles were constructed for 55, 70 and 85°C from the first-order rate constants obtained from isothermal studies at pH values ranging from 1.71 to 10.00. The pH-rate profile indicated that famotidine undergoes specific acid catalysis in the acidic region and general base catalysis in the alkaline region. Hydrolysis in the acidic and alkaline media resulted in the formation of four and five degradation products, respectively. A possible degradation pathway for the acidic and alkaline hydrolysis was discussed.
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    Hydroxypropyl-β-Cyclodextrin Increases the Aqueous Solubility and Stability of Pilocarpine Prodrugs (1995)
    Springer
    Pharmaceutical research 12 (1995), S. 1371-1375 
    Details
    ISSN: 1573-904X
    Keywords: prodrug ; bispilocarpic acid diester ; hydroxypropyl-β-cyclodextrin ; inclusion complex ; solubility ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. The effects of 2-hydroxypropyl-β-cyclodextrin (HP-β-CD) on the aqueous solubility and stability of two lipophilic bispilocarpine prodrugs were investigated at pH 7.4. Methods. The solubility of prodrugs was studied by phase-solubility method (0–72.5 mM HP-β-CD). The stability of one of the prodrugs was investigated as a function of temperature (40°C–70°C) and HP-β-CD concentration (0–72.5 mM). The apparent rate constants (k 1, k 2) for degradation of prodrug in 1:1 and 1:2 inclusion complexes and apparent stability constants (K 1:1, K l:2) were calculated by the curve-fitting method. Results. The phase-solubility diagrams were classified as Ap-type and the apparent stability constants (K l:l, K l:2) for 1:1- and 1:2-inclusion complexes were calculated to be 143–815 M−l and 29–825 M−1, respectively. The stability of prodrug increased as a function of HP-β-CD concentration over the studied temperature range. The shelf-life (t 90%, calculated by the Arrhenius equation) of the prodrug in 72.5 mM HP-β-CD solution increased 5.1-fold and 6.1-fold at 25°C and 4°C, respectively. Conclusions. The solubility of the prodrugs was shown to increase markedly in phase-solubility studies. The degradation rate of prodrug in stability studies was shown to be slower in the l:2-complex than in the l:l-complex and the relative amounts of complex species were found to be dependent on CD concentration.
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    The Distribution of Oleic Acid Between Salbutamol Base Drug and Different Propellant Blends (1995)
    Springer
    Pharmaceutical research 12 (1995), S. 715-719 
    Details
    ISSN: 1573-904X
    Keywords: salbutamol base drug ; oleic acid ; propellant ; metered-dose inhaler ; stability ; adsorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The distribution of oleic acid between Salbutamol base drug and the solvent in metered-dose inhalers (MDI's) has been investigated. The equilibrium surfactant concentration in the drug dispersions has been determined using a colorimetric method. The samples examined contained Salbutamol base drug particles and oleic acid dispersed in different propellant blends of freon 11 and 12. The maximum equilibrium concentration observed depended on the propellant blend used. The propellant blend and the distribution of the surfactant affected the dispersion stability. The effect of the surfactant is illustrated by the adsorption isotherm for oleic acid onto the Salbutamol particles. The results are correlated with zeta-potentials and particle size measurements made on similar systems in order to characterize the properties of surfactant stabilized MDI's.
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    Some Factors Associated with the Ultrasonic Nebulization of Proteins (1995)
    Springer
    Pharmaceutical research 12 (1995), S. 53-59 
    Details
    ISSN: 1573-904X
    Keywords: aerosol ; lactate dehydrogenase ; nebulizers ; proteins ; ultrasonic nebulization ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Ultrasonic nebulization of lactate dehydrogenase (LDH) was investigated using a DeVilbiss “Aerosonic” nebulizer. The enzyme (8ml, 0.025mg/ml Na2HPO4, pH 7.0) was completely inactivated after 20 minutes of operation. However, the inactivation profile observed during ultrasonic nebulization was different from that previously observed using air-jet nebulization. At least two mechanisms are involved, one associated with heating and the other with aerosol production. By preventing heating of the nebulizer fluid during operation, the denaturation profile was dramatically altered. By additionally including 0.01% w/v Tween 80 or l%w/v PEG 8000, almost all activity was retained. Similar results were obtained by preventing aerosol production and heating. However, 100% of activity was lost when heating was allowed to occur without aerosol formation. The results demonstrate that cooling in conjunction with a surfactant is one approach that could be used to stabilize proteins to ultrasonic nebulization. However, cooling also significantly reduced solute output from the nebulizer. When operated at 10°C output was negligible. At 50°C the output was 5× greater than that found at room temperature. The median droplet size (µm) was not significantly influenced by the operating temperature of the nebulizer fluid (3.6 ± 0.4, 21°C; 3.9 ± 0.2, 50°C, p = NS (n = 6)) although the size distribution was noted to increase at the higher temperature.
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    The Importance of Structural Factors on the Rate and the Extent of N,O-acyl Migration in Cyclic and Linear Peptides (1995)
    Springer
    Pharmaceutical research 12 (1995), S. 323-328 
    Details
    ISSN: 1573-904X
    Keywords: acyl migration ; peptides ; cyclosporin ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The chemistry associated with the process of N,O-acyl migration was explored in both cyclic and linear peptides under aqueous acid conditions. The importance of backbone cyclization and N-methylation of the peptide bond on the kinetics of N,O-acyl migration in a series of linear and cyclic peptides related in structure to cyclosporin A (CsA) were examined. The similarity in the chemical reactivity of the cyclic peptide [MeLeu (3-OH)]1-CsA and the corresponding linear peptide [Val-MeLeu (3-OH)-Abu], suggested that for this series, cyclization of the peptide backbone may not play an important role in controlling the kinetics of N,O-acyl migration. In contrast, the disparity in the chemical reactivity of tripeptides [Val-MeLeu (3-OH)-Abu] and [Val-Leu (3-OH)-Abu], indicated that N-methylation of amide bond significantly impacted the kinetics. Various hypothesis are proposed to account for this observation.
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    URL: http://dx.doi.org/10.1023/A:1016231913858
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    Stabilization of Chimeric BR96-Doxorubicin Immunoconjugate (1995)
    Springer
    Pharmaceutical research 12 (1995), S. 215-222 
    Details
    ISSN: 1573-904X
    Keywords: chimeric antibody ; protein ; immunoconjugate ; lyophilization ; freeze-drying ; stability ; aggregation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Chimeric BR96-doxorubicin conjugate (BR96-DOX) is an immunoconjugate designed to specifically target and kill certain tumor cells. The linker between the chimeric BR96 antibody and DOX is an acid-labile hydrazone group which was designed to undergo lysosomal hydrolysis to release DOX in vivo. Stability studies indicated that acid-catalyzed hydrazone hydrolysis was the major degradation route in vitro. Even under optimal conditions of pH and temperature, the stability of BR96-DOX in solution was not acceptable for long-term storage. Lyophilization of BR96-DOX in the presence of added sugars, such as lactose or sucrose, and subsequent storage of the lyophile under refrigeration significantly improved the stability. Therefore lyophilization appears to be a viable approach for achieving long-term stabilization of BR96-DOX.
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    URL: http://dx.doi.org/10.1023/A:1016274825322
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    Chemical Pathways of Degradation of the Bradykinin Analog, RMP-7 (1995)
    Springer
    Pharmaceutical research 12 (1995), S. 305-308 
    Details
    ISSN: 1573-904X
    Keywords: RMP-7 ; bradykinin ; stability ; diketopiperazine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1023/A:1016203731682
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    Effects of riblets upon flow stability (1995)
    Springer
    Flow, turbulence and combustion 54 (1995), S. 313-321 
    Details
    ISSN: 1573-1987
    Keywords: riblets ; stability ; Tollmien-Schlichting ; Görtler
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The onset of transition in the boundary layer over a grooved surface is studied by introducing the presence of grooves into the standarde 9 model with the aid of a previously obtained equivalent boundary condition. Under conditions of self-similarity and smallness of the grooves, Tollmien-Schlichting waves are found to be excited at a slightly smaller Reynolds number and Görtler vortices at a slightly larger one than on a smooth surface.
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    A microstructural investigation of the nonlinear response of electrorheological suspensions (1995)
    Springer
    Rheologica acta 34 (1995), S. 417-429 
    Details
    ISSN: 1435-1528
    Keywords: Electrorheology ; nonlinear ; simulations ; stability ; steady shear
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract Particle-level simulations are employed to investigate the transition from linear to nonlinear rheological behavior for electrorheological suspensions under start-up of steady shear flow. This transition is found to first arise from the very slight rearrangement of structures, as opposed to the gross rupture of particulate columns. Linear stability analysis shows that these rearrangements occur when the structures are sheared into electrostatically unstable configurations. The rearrangements also produce a second type of relaxation phenomenon that appears at low frequencies and finite strain amplitudes. Incorporating more realistic force descriptions into the idealized simulation model shifts the transition to nonlinear deformation to smaller strain amplitudes, approaching experimentally observed values. The role of the rearrangement of unstable structures on the oscillatory shear flow response is investigated in the following paper, Part II.
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    A microstructural investigation of the nonlinear response of electrorheological suspensions (1995)
    Springer
    Rheologica acta 34 (1995), S. 430-439 
    Details
    ISSN: 1435-1528
    Keywords: Electrorheology ; nonlinear ; simulations ; stability ; viscoelasticity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract In the preceding paper, Part 1, the transition from linear to nonlinear behavior for electrorheological (ER) suspensions under start-up of steady shear flow was found to first arise from the slight rearrangement of unstable structures. In this paper, we investigate the transition to nonlinear behavior for ER suspensions under oscillatory shear flow, focusing on the role of the rearrangement of unstable structures, and employing experimental and simulation results. Again, we find that nonlinear deformation first arises from these rearrangements, as opposed to the gross rearrangement or rupture of particulate chains. The Fourier transform of the simulated time-dependent shear stress is employed to quantify the dependence of the critical strain on the deformation frequency and electric field strength. The predicted behavior is consistent with experimental trends. Methods for verifying the predictions are discussed, as well as possible avenues for exploiting this information in improved operating strategies and improved ER fluids.
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    Masthead (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995) 
    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.19951280101
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    Tripodal Triamidostannates as Building Blocks in the Generation of Sn - M-Bonded Heterobimetallics (M = Fe, Ru) (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 29-34 
    Details
    ISSN: 0009-2940
    Keywords: Tripodal ligands ; Triamidostannates ; Metal-metal bonds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By in situ lithiation of the trifunctional amines H3CC(CH2NHSiMe3)3, PhC(CH2NHSiMe3)3, and HC{SiMe2NH(p-Tolyl)}3 and subsequent reaction with SnCl2 the corresponding triamidostannates were obtained. These were coupled with CpM(CO)2Cl (M = Fe, Ru) to yield the M - Sn-bonded heterobimetallics 9-14 of which H3CC(CH2NSiMe3)3SnFe(CO)2Cp (9) was characterized by a single-crystal X-ray structure analysis. Of the in situ-generated amidostannates only [HC{SiMe2N(p-Tolyl)}3Sn][Li(THF)3] (8) could be isolated as a uniform product and characterized analytically and spectroscopically.
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    The Structures of [X2Y—N—YX2]+ Cations (X = F, Cl; Y = S, Se). A Comparison of X-ray and ab Initio Studies[1] (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 35-40 
    Details
    ISSN: 0009-2940
    Keywords: Selenium-nitrogen compounds ; Sulfur-nitrogen compounds ; Calculations, ab initio ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structures of cationic species of the series [X2Y—N—YX2]+ (X = F, Cl; Y = S, Se) have been computed ab initio using all electron treatments for first-row elements and sulfur and quasi-relativistic pseudopotentials for Se and Cl. Splitvalence basis sets with polarization and diffuse functions were employed. The MP2 results for the (non-isostructural!) cations [Cl2Se—N—SeCl2]+ (1: Cs) and [F2S—N—SF2]+ (2: C2v) are in excellent agreement with the experimental (X-ray) observations. Both structures represent local minima. A deeper minimum for either of the cations is represented by another C2v isomer which for crystal lattice energy reasons is stable in the isolated state only. The geometries of the hitherto unknown species [Cl2S—N—SCl2]+ (3) and [F2Se—N—SeF2]+ (4) have been assessed by ab initio HF calculations. In analogy to 2, cations 3 and 4 are predicted to prefer C2v symmetry. Therefore, 1 exhibits unusual structural features. According to strictly localized natural bond orbital analysis (NBO), the central nitrogen atoms in 1 and 2 possess two lone pairs of electrons (LP: one sp hybrid and one p orbital). The relatively short Se—N and S—N bond distances in 1 (1.741-1.760 Å) and 2 (1.551 Å) can best be attributed to LP(N)→s̰*(Y—X) negative hyperconjugation (1: Y = Se, X = Cl; 2: Y = S, X = F).
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19951280106
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    Die fördernde Rolle von Phosphinoester-Liganden bei der Synthese neutraler Carben-, Vinyliden- und Allenyliden-Ruthenium(II)-KomplexeHerrn Professor Hubert Schmidbaur zum 60. Geburtstag gewidmet. (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 49-62 
    Details
    ISSN: 0009-2940
    Keywords: Ruthenium(II) complexes, octahedral ; Phosphino esters as mono- and bidentate ligands ; Fluxional behaviour ; Carbene complexes ; Vinylidene complexes ; Allenylidene complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vinylidene Transition-Metal Complexes, XXXV[1].  -  The Supporting Role of Phosphino Ester Ligands for the Synthesis of Neutral Carbene, Vinylidene and Allenylidene Ruthenium(II) ComplexesThe reaction of [RuCl2(PPh3)3] (1) with the phosphino esters iPr2P(CH2)nCO2R (2-4) leads to complete (n = 1; R = CH3, C2H5) or partial (n = 2; R =CH3) displacement of the PPh3 ligands and formation of the octahedral ruthenium(II) complexes [RuCl2{k2(P,O)-iPr2PCH2CO2R}2] (5, 6) and [RuCl2(PPh3){k(P)-iPr2PCH2CH2CO2Me}{k2(P,O)-iPr2PCH2CH2CO2Me}] (7). Treatment of 5 with LiBr and LiI affords the dibromo- and diiodoruthenium derivatives 8 and 9. While compound 5 reacts with CO and SO2 by cleavage of one Ru - O bond to yield the 1:1 adducts [RuCl2(L){k(P)-iPr2PCH2CO2Me}{k2(P,O)-iPr2PCH2CO2Me}] (10, 11), the reaction of the dibromo derivative 8 with CO in solution gives the dicarbonyl complex [RuBr2(CO)2{k(P)-iPr2PCH2CO2Me}2](13). If CO is passed over 8 in the solid state, the corresponding monocarbonyl compound 14 is formed. The hydridoruthenium(II) complex 16, which is obtained from equimolar amounts of [RuHCl(CO)(PiPr3)2] (15) and 2, reacts with HC≡CMe by insertion to give the vinyl derivative [RuCl{E - CH=CHMe}(CO)(PiPr3){k2(P,O)-iPr2CH2CO2Me}] (17). Treatment of 5 with HC̊' (R' = H, Me, tBu, Ph) and of 6, 8, 9 with HC≡CPh affords upon photochemical activation the octahedral vinylidene complexes [RuX2-(=C=CHR){k(P)-iPr2PCH2CO2R}{k2(P,O)-iPr2PCH2CO2R}] (18-21 and 23-25) in good to excellent yield. At room temperature, these compounds (with the exception of 25) are highly fluxional in solution. From 31P-NMR measurements, the free energies of activation ΔG
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    Reaktionen von R2Al—AlR2 (R = CH(SiMe3)2) mit Trimethylsilylazid  -  Insertion in die Al—Al-Bindung und Abbau zum trimeren Dialkylaluminiumazid (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 81-85 
    Details
    ISSN: 0009-2940
    Keywords: Aluminium-aluminium bond ; Insertion of trimethylsilyl azide ; Trimeric dialkylaluminium azide ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of R2Al—AlR2 (R = CH(SiMe3)2) with Trimethylsilyl Azide  -  Insertion into the Al—Al Bond and Formation of a Trimeric Dialkylaluminium AzideTetrakis[bis(trimethylsilyl)methyl]dialuminium(4) (1) reacts with trimethylsilyl azide under insertion of one nitrogen atom into the Al—Al bond. As shown by NMR spectra and crystal structure the product contains three and four coordinated Al atoms due to the coordination of the α-nitrogen atom of the azide group to one of the Al atoms. An electronically delocalized N3-system is formed with a N—N bond length of 132.0 pm and a bond order of 1.5 for both N—N bonds. With an excess of trimethylsilyl azide further reaction is observed only under mild irradiation conditions with an exchange of the azide group between Si and Al and formation of Me6Si2 and the dialkylaluminium azide 3, which is better synthesized by the reaction of Me3Si—N3 with Cl—Al[CH(SiMe3)2]2. The sterically highly shielded aluminium azide 3 is a trimer in the solid state showing a non-planar 12-membered Al3N9 heterocycle with short N—N bonds (114 pm).
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    URL: http://dx.doi.org/10.1002/cber.19951280112
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    Transition-Metal Complexes with the Novel Scorpionate Ligand Dihydrobis-(tetrazolyl)borate: Synthesis and Characterization of Infinite Two-Dimensional Metal-Ligand Frameworks and One-Dimensional Water SubstructuresDedicated to Professor Dr. Herbert Schumann on the occassion of his 60th birthday. (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 323-328 
    Details
    ISSN: 0009-2940
    Keywords: Poly(azolyl)borates, metal complexes of ; Bis(tetrazolyl)borate, metal complexes of ; Metal-nitrogen coordination ; Coordination polymers ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dihydrobis(tetrazolyl)borate metal compounds of the composition [M(L)2{μ-H2B(CHN4)2}2]n for M = Mn, Fe, Co, Zn, Cd with L = H2O and for M = Cu with L = NH3 are obtained from metal salts and K[H2B(CHN4)2]. Single-crystal X-ray studies reveal the formation of two-dimensional rhombic grid sheets through the bridging action of the bis(tetrazolyl)borate ligands. Each metal atom is octahedrally coordinated with two trans L ligands and four H2B(CHN4)-2 nitrogen donors. Two additional, hydrogen-bonded water molecules occupy the rhombic openings in the compounds with M = Mn, Fe, Co, Zn, and Cd. The water of crystallization is held in place through hydrogen bonding from the water ligands and to the nitrogen atoms to give a substructure of parallel kinked water chains. Temperature-variable magnetic measurements show a Curie-Weiss behavior for the paramagnetic complexes with M = Mn, Fe, Co, and Cu.
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    New Organophosphorus Ligands: Cyclopropanation and Other Reactions of Cumulenes Bearing Diphenylphosphanyl Substituents (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 365-371 
    Details
    ISSN: 0009-2940
    Keywords: Cumulenes ; Butadienes ; Vinylcyclopropane ; Vinylidenecyclopropane ; Bicyclopropyl, phosphanyl-substituted ; Cyclopropanation ; Phosphane ligands ; Phosphane chalcogenides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydrophosphorylation of 1,4-bis(diphenylphosphanyl)butadiyne with diphenylphosphane leads to the butadiene (Ph2P)2C=CH—CH=C(PPh2)2 (1). Treatment of 1 with dimethylsulfonium methylide gives the vinylcyclopropane (Ph2P)2C=CH—CH(CH2)C(PPh2)2 (2). Compound 2 reacts with aqueous hydrogen peroxide, elemental sulfur, or selenium to afford the tetrachalcogenides (Ph2XP)2C=CH—CH(CH2)C(PXPh2)2 with X = O (3), X = S (4), X = Se (5), respectively. While the tetraphosphane 1 and the vinyl-cyclopropane compound 2 cannot be converted into a bis-(cyclopropyl) compound with an excess of Me2S=CH2, the tetrasulfide 4 readily affords a mixture of (1R,1′R)-/(1S,1′S)-and meso-2,2,2′,2′-tetrakis(diphenylthiophosphinyl)-1,1′-bicyclopropyl (6, 7) in good yield. Treatment of 1,1,4,4-tetrakis-(diphenylphosphanyl)butatriene with dimethylsulfonium methylide leads to the vinylidenecyclopropane (Ph2P)2C=C=C(CH2)C(PPh2)2 (8). Compound 8 is converted into its tetrasulfide (Ph2SP)2C=C=C(CH2)C(PSPh2)2 (9) by treatment with elemental sulfur. The crystal structures of 1, 2, 4, 7, and 8 have been determined by single-crystal X-ray diffraction.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19951280408
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    Mono- und Diferriophosphane und -thioxophosphoraneHerrn Professor Dr. Ekkehard Lindner zum 60. Geburtstag gewidmet. (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 413-416 
    Details
    ISSN: 0009-2940
    Keywords: Ferriophosphanes ; Ferriophosphoranes ; Thioxophosphane ligand ; Decarbonylation reaction ; Sulfurization ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mono- and Diferriophosphanes and -thioxophosphoranesHerrn Professor Dr. Ekkehard Lindner zum 60. Geburtstag gewidmet.The substitution of organic substituents in phosphanes or thioxophosphoranes by the 17-electron fragments CpFe-(CO)2 (—Fp) leads to isolobal ferriophosphanes or -thioxophosphoranes. The mono- and diferriophosphanes FpnPPh3-n [n = 1 (3), 2 (4)] are obtained by deprotonation of the mono- and diferriophosphonium salts [FpnPPh3-nH]X [n = 1 (1), 2 (2)] with DBU. They are oxidized by sulfur giving the mono- and diferriothioxophosphoranes FpnPPh3-n(S) [n = 1 (5), 2 (6)]. Sulfide 5 arises also from the reaction of CpFe(CO)2Cl and Ph2PH(S)/DBU. The one-sided decarbonylation reaction of 6 leads to FpFp′PPh(S) (7, Fp′ = CpFeCO). The Fp substituents (17 electrons) in 3-7 coordinate as one-electron donors to the PhnP- or PhnP(S) units (n = 1, 2). The bridging functions in 4 and 6 are hitherto unknown. The molecular structures of the complexes 5-7 were determined by X-ray structure analyses.
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    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.
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    URL: http://dx.doi.org/10.1002/cber.19951280417
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    Synthesis and Structure of the First Dimetalated Diphosphane Disulfide [(η5-C5Me5)(CO)2FeP(H)(S)]2 (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 441-442 
    Details
    ISSN: 0009-2940
    Keywords: Diphosphane disulfides ; Metallophosphoranes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The first transition metal derivative meso-[(η5-C5Me5)(CO)2FeP(H)(S)]2 (2) of the unknown diphosphane disulfide [PH2(S)]2 results from treatment of (η5-C5Me5)(CO)2FePH2 (1) with 1.5 equivalents of elemental sulfur. Compound 2 was characterized by means of spectroscopy (IR, 31P, 31P{1H}, 13C{1H}, 1H NMR) as well as X-ray diffraction analysis.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19951280419
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    Preparation and Molecular Structures of Tetrahydrofuran, Diethylene Diglycol Dimethyl Ether and 18-Crown-6 Complexes of Strontium and Barium TetrahydridoborateDedicated to Prof. Dr. Nils Wiberg on the occasion of his 60th birthday. (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 455-460 
    Details
    ISSN: 0009-2940
    Keywords: Strontium bis(tetrahydridoborate)-2 tetrahydrofuran, chain polymer of ; Strontium bis(tetrahydridoborate)-bis(diglyme) ; Barium bis(tetrahydridoborate)-bis(diglyme) ; Strontium bis(tetrahydridoborate)-1,4,7,13,16-hexaoxacyclooctadecane ; Metal-hydrogen-boron bridges ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The strontium and barium tetrahydridoborate complexes M(BH4)2 · 2 diglyme and M(BH4)2 · 18-crown-6 (M = Sr, Ba) have been prepared from the solvates M(BH4)2 · 2 THF by ligand displacement. 11B-NMR and IR data reveal strongly polar bonding of the BH4 groups to the metal centers, and X-ray structural analyses of the diglyme and crown ether compounds show molecular units in which the BH4 group is in contact via three H atoms with the metal center. In contrast, M(BH4)2 · 2 THF compounds are chain polymers in the solid state, and each metal center is surrounded by 2 THF molecules in trans position and four BH4- groups each of which forms bridges with two metal centers. Estimations of the effective radius for the BH4 group indicate a high polarity for the M-BH4 interaction.
    Additional Material: 4 Ill.
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    Photochemische Reaktionen von Übergangsmetall-Organyl-Komplexen mit Olefinen, 1312. Mitteilung: Lit.Photochemisch induzierte [5+2],homo[5+21-Cycloaddition von 3-Hexin an Tricarbonyl(η5-2,4-cycloheptadien-l-yl)mangan (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 515-518 
    Details
    ISSN: 0009-2940
    Keywords: Manganese ; Cycloheptadienyl ; Alkyne ; [5+2],homo[5+2] Cycloadditions ; Tricyclo[5.3.1.04,10]undeca-2,5-dien-11-yl ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photochemical Reactions of Transition Metal Organyl Complexes with Olefins, 1312. Mitteilung: Lit. . - Photochemically Induced [5+2], homo[5+2] Cycloaddition of 3-Hexyne to Tricarbonyl(η 5-2,4-cycloheptadien-1-yl)manganeseTricarbonyl(η5-2,4-cycloheptadien-1-yl)manganese (1) reacts upon UV irradiation in hexane at 243 K with two equivalents of 3-hexyne (2) in successive [5+2],homo[5+2] cycloadditions to give tricarbonyl(η2:2:1-1,2,3,11-tetraethyltricyclo-[5.3.1.04,10]undeca-2,5-dien-11-yl)manganese (3). Its crystal and molecular structure was determined by an X-ray diffraction analysis, in solution it was studied also by IR and NMR spectroscopy.
    Additional Material: 1 Ill.
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    Masthead (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280601
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    1,4,2-Diazaphospholothiazoles and -pyridines by a Hantzsch-Type Condensation Using Chloromethyldichlorophosphane (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 581-587 
    Details
    ISSN: 0009-2940
    Keywords: Anellated azaphospholes ; Hantzsch-type [3 + 2] cyclocondensation ; Chloromethyldichlorophosphane ; Regioselectivity ; 31P-, 1H-, 13C-NMR spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The [3 + 2] cyclocondensation of 2-amino-1,3-thiazoline, 2-aminopyridines, 2- and 4-aminopyrimidines, 2-aminopyrazine, and 2-aminoquinoline with chloromethyldichlorophosphane in the presence of triethylamine yields regiospecifically 5,6-dihydrothiazolo[2,3-e][1,4,2]diazaphosphole (3), 1,4,2-diazaphospholo[4,5-α]pyridines (12), 1,4,2-diazaphospholo[4,5-α]pyrimidines (15), 1,4,2-diazaphospholo[4,5-e]pyrimidine (17), 1,4,2-diazaphospholo[4,5-α]pyrazine (19), and [1,4,2]diazaphospholo[4,5-α]quinoline (22), respectively. Using 2-amino-1,3-thiazole (4) and 2-aminobenzothiazoles 8, we obtained mixtures of the 1,5- and 4,5-anellated 1,4,2-diazaphospholes 5/6, 9a/10a and 9b/10b, while in the case of the methyl derivative 8c only the [1,4,2]diazaphospholo[5,4-b][1,3]benzothiazole 10c was formed. In the reaction of 2-aminothiazole and 2-aminopyrazine with Chloromethyldichlorophosphane the bis(diazaphospholo)-substituted chloromethylphosphanes 7 and 20 could be detected. The new anellated 1,4,2-diazaphospholes are colorless to pale yellow crystalline moisture-sensitive solids.
    Additional Material: 6 Tab.
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    Reactions at Silicon-Silicon Bonds, V. Selective Trichlorosilylation of Alkyl(diorganylamino)chlorophosphanes with Hexachlorodisilane or with Trichlorosilane/Triethylamine. - Two Routes to New Functional Trichlorosilylphosphanes (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 615-619 
    Details
    ISSN: 0009-2940
    Keywords: Reductive silylation ; Aminochlorophosphanes ; Silylphosphanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of alkyl(diorganylamino)chlorophosphanes R(R2′N)PCl 1 (1a: R = tBu, R′ = Et, 1b: R = iPr, R′ = iPr; 1c: R = iPr, R′ = Ph) with hexachlorodisilane, afforded alkyl(diorganylamino)trichlorosilylphosphanes R(R2′N)PSiCl3 2 (2a: R = tBu, R′ = Et; 2b: R = iPr, R′ = iPr; 2c: R = iPr, R′ = Ph) and silicon tetrachloride. An intermediate formed in the reaction of 1b with hexachlorodisilane, the adduct iPr(iPr2N)(Cl)P-Si(Cl)3-SiCl3 (3b = 1b · Si2Cl6), was detected by 31P- and 29Si-NMR spectra that indicate pentacoordinated silicon bound to tetracoordinated phosphorus and tetracoordinated silicon. Trichlorosilylphosphanes 2 are also available from 1 under very mild conditions by reductive trichlorosilylation with trichlorosilane in the presence of triethylamine. Compounds 2 were identified analytically, by mass spectroscopy, multinuclear NMR, and an X-ray structure determination of 2c.
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    Reactions of Complex Ligands, LXIVPart LXIII: Ref.. Synthesis of 5,5′-Diphenyl-2,2′-bifuran, a Biaryl Compound with Remarkable Fluorescence Properties (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 641-643 
    Details
    ISSN: 0009-2940
    Keywords: Carbene ligands ; Tungsten complexes ; 2,2′-Bifuran ; Copper coupling reaction ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 2-oxacyclic α,β-unsaturated carbene complex 1 reacts with an excess of dimethylamine to give the diphenylbifuran 2. The structure of 2 was established by independent synthesis from 2-phenylfuran (4) via regioselective lithiation and transmetalation to zinc and tin organometallics 6a-c and final oxidative copper coupling reactions.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19951280618
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    Synthesis of 2- and 3-Stannolenes via Addition of Trimethyltin Alkoxides to 3-Diethylboryl-4-ethyl-1,1-dimethylstannole (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 679-687 
    Details
    ISSN: 0009-2940
    Keywords: Stannole, diethylboryl-substituted ; Trimethyltin alkoxides ; 2-, 3-Stannolenes, organometallic-substituted ; NMR, coupling constants, 2J(Sn,Sn), sign determination ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Trimethyltin alkoxides (2) react stereoselectively with 3-diethylboryl-4-ethyl-1,1-dimethylstannole (1) via addition of the Me3Sn group to C(2) to the C(2) = C(3) bond and a 1,2 shift of an ethyl group from boron to C(3) to give the 2-stannolenes 3. The molecular structure of 3f' [R = (S)-2-Bu] was determined by single-crystal X-ray analysis, confirming the cis positions of the Et(RO)B and the Me3Sn group. These 2-stannolenes 3 undergo, upon heating to ca. 80°C, facile rearrangement by irreversible allylic migration of the Et(RO)B group to the 3-stannolenes 4 in which the cis positions of the boryl and the stannyl group are retained. All 2-stannolenes (in contrast to the 3-stannolenes) are readily deprotoborylated to give the 3-stannolene 5. The structures of 3, 4, and 5 follow conclusively from 1H-, 11B-, 13C-, and 119Sn-NMR spectra. The negative sign of the geminal coupling constants 2J(SnSn) was determined in the case of 3, 4, and 5 by 2D 119Sn/1H heteronuclear shift correlations.
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    Synthesis of Structures of (Acyloxy)boranesDedicated to Prof. Dr. A. Schmidpeter on the occasion of his 65th birthday.Synthesis of Structures of (Acyloxy)boranes (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 751-762 
    Details
    ISSN: 0009-2940
    Keywords: Trifluoroacyloxy-9-borabicyclo[3.3.1]nonane ; Pivaloyloxy-9-borabicyclo[3.3.1]nonane dimer ; Bis(9-borabicyclo[3.3.1]nonyl]oxalate ; Tetrakis(9-borabicyclo[3.3.1]nonyl)-dihydroxyoxalate ; Bis(9-borabicyclo[3.3.1]nonyl)-2,2-dimethylmalonate tetramer ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 9-Borabicyclo[3.3.1]nonane (9-BBNH) reacts with monocarboxylic acids to afford 9-(acyloxy)-9-borabicyclo[3.3.1]nonanes which are dimers in the solid state as shown by X-ray crystal structures of the benzoate and pivalate. More complex reactions were observed by allowing 9-BBNH to react with dicarboxylic acids in THF or monoglyme. Thus, (9-BBN)2 oxalate 3 contains a fully delocalized oxalate unit with equal C-O and B-O bond lengths. Traces of water convert it into the tetrakis(9-BBN) oxalate 5. A rather unusual structure is veryfied by 9-BBN 2,2-dimethylmalonate 7 which according to its molecular structure is a tetramer featuring a 32-membered ring system. In contrast, reactions of oxalic acid with thexylborane leads to reduction of the acid and formation of a bicyclic dioxaborolo-dioxaborolane 10. Several intermediates were detected by 11B-NMR spectroscopy as well as in reactions of BH3 · THF or BH3 · SMe2 with oxalic acid.  -  It follows from the present study that (acyloxy)boranes derived from dicarboxylic acids are strong Lewis acids with an unexpected variety of structural features.
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    A T-Shaped Selenenyl Halide: Synthesis and Characterisation of a Proposed Reaction Intermediate (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 741-742 
    Details
    ISSN: 0009-2940
    Keywords: Selenenyl halides ; Nucleophilic substitution ; Complex intermediate ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The T-shaped selenenyl halide (1), which may be regarded as a model substance for the transition state in nucleophilic displacement at divalent chalcogen atoms, has been isolated and subjected to X-ray structure determination.
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    Zinc Complexes of Drugs Containing Nitrogen Heterocycles (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 779-785 
    Details
    ISSN: 0009-2940
    Keywords: Zinc complexes ; Drug ligands ; Captopril ; Isoniazid ; Nalidixic acid ; Mercaptopurine ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four drugs whose actions have a relation to the status of zinccontaining species in the human body were used as ligands in zinc complexes. Captopril (H2Cap) forms the compound [ZnCap] (1) presumed to be a coordination polymer with O and S coordination. Isoniazid, in the presence of zinc salts, is converted to 1,2-diisonicotinoyl hydrazide (H2Nih) which forms polymeric [Zn(Nih)NH3] (2) with trigonal-bipyramidal ZnO2N3 coordination. Nalidixic acid (HNal) and zinc perchlorate yield [Zn(HNal)2(H2O)2](ClO4)2 · 2 H2O (3) containing zinc in an octahedral ZnO6 environment. Mercaptopurine (H2Mer), in the presence of ammonia, forms [Zn(Mer)(NH3)2] . H2O (4) which is a coordination polymer containing tetrahedral ZnN4 units. The structures of [Zn(Nih)NH3], [Zn(HNal)2(H2O)2](ClO4)2 . 2 H2O, and [Zn(Mer)(NH3)2] . 2 H2O were determined diffractometrically.
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    Enantioselective Deprotonation of Benzyl Phosphates by Homochiral Lithium Amide Bases  -  Configurational Stability of Benzyl Carbanions with a Dialkoxyphosphoryloxy Substituent and Their Rearrangement to Optically Active α-Hydroxy Phosphonates (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 823-830 
    Details
    ISSN: 0009-2940
    Keywords: Phosphate-phosphonate rearrangement ; Carbanions, benzylic, configurational stability of ; Phosphonaes Lithium amides, homochiral ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Benzyl dialkyl phosphates are deprotonated enantioselectively by homochiral lithium amides of isopropyl(1-phenylethyl)amine or bis(1-phenylethyl)amine. The short-lived benzylic carbanions formed are virtually configurationally stable relative to the rearrangement to optically active phenyl-hydroxymethylphosphonates. The enantiomeric excesses are up to 50%. The pro-(S) hydrogen is removed by amides having (S) configuration. Homochiral diethyl (S)-phenyl[D1]-methyl phosphate [(S)-16c] is deprotonated by both LDA and n-BuLi with a high primary kinetic isotope effect (kH/D ≍ 50) and isomerizes to the corresponding α-hydroxy phosphonate with an enantiomeric excess of up to 85%.
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    Tris(1,10-phenanthroline)iron(II) Complexes  -  Broad Variation of the Redox Potential by 4,7-Substitution at the Phenanthroline Ligands[1] (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 845-850 
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    ISSN: 0009-2940
    Keywords: Phenanthroline synthesis ; Tris(phenanthroline)iron(II) complexes ; Redox potential ; Cyclic voltammetry ; Electron transfer, outer-sphere ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new 4,7-donor-substituted phenanthrolines 2a-h were synthesized and the corresponding tris(1,10-phenanthroline)iron(II) complexes 3a-h studied by cyclic voltammetry. In more detail three novel aza-crown ether-linked (phenanthroline)iron complexes were investigated, the redox potentials of which could be fine-tuned by the addition of group-Ia,IIa metal cations. All iron(II) complexes showed reversible waves at scan rates between 50 and 500 mV · s-1 and could be reversibly oxidized and reduced by chemical means.
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    Bis(cyclopentadienyl)methane-Bridged Dinuclear Complexes, 10Part 9: B. Stempfle, H. Werner, Gazz. Chim. Ital., 1995, 125, in press. The Bis(cyclopentadienyl)methane Link between Lewis Basic and Lewis Acidic Metal CentersDedicated to Prof. Dr. Herbert Schumann on the occasion of his 60th birthday. (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 877-881 
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    ISSN: 0009-2940
    Keywords: Bis(cyclopentadienyl)methane ; Heterobimetallic complexes ; Imido complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mononuclear rhodium complexes [(C5H5CH2C5H4)-Rh(CO)2] (1) and [(C5H5CH2C5H4)Rh(PhC≡CPh)(PiPr3)] (2) readily react with nBuLi or TlOEt to yield the corresponding lithium salts 3 and 4 or thallium salts 5 and 6. The reaction of these salts with [(C5H5)Nb(NtBu)Cl2] (7) leads to the formation of the heterodinuclear compounds [{CH2(C5H4)2}-{Rh(CO)2}{(C5H5)Nb(NtBu)Cl}] (8) and [{CH2(C5H4)2}-{Rh(PhC≡CPh)(PiPr3)}{(C5H5)Nb(NtBu)Cl}] (9), respectively. Treatment of 3-6 with [Mo(NtBu)2Cl2] (10) gives the heterodinuclear Rh/Mo complexes [{CH2(C5H4)2}{Rh(CO)2}-{Mo(NtBu)2Cl}] (11) and [{CH2(C5H4)2}{Rh(PhC≡CPh)-(PiPr3)}{Mo(NtBu)2Cl}] (12). The analogous reaction of [Mo(NMes)2Cl2(DME)] (13) with 3-6 yields the corresponding complexes [{CH2(C5H4)2}{Rh(CO)2}{Mo(NMes)2Cl}] (14) and [{CH2(C5H4)2}{Rh(PhC≡CPh)(PiPr3)}{Mo(NMes)2Cl}] (15). From the monometallated ligand [(C5H5CH2C5H4)M] (M = Li: 16; M = Tl: 17) and the imidometal compounds 7, 10 and 13, the mononuclear complexes [(C5H5CH2C5H4)(C5H5)Nb-(NtBu)Cl] (18) and [(C5H5CH2C5H4)Mo(NR)2Cl] (R = tBu: 19; R = Mes: 20) have been obtained.
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    Addition von Hydrofullerid [C60H]- an koordinierte, ungesättigte Kohlenwasserstoffe: Bindung von Fulleren an Metallkomplexe über KohlenwasserstoffbrückenHerrn Professor Herbert Walter Roesky zum 60. Geburtstag gewidmet (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1059-1060 
    Details
    ISSN: 0009-2940
    Keywords: Fullerene ; Hydrofulleride ; Manganese complex ; Rhenium complex ; Iron complexes ; Ruthenium complex ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Addition of Hydrofulleride [C60H]- to Coordinated, Unsaturated Hydrocarbons: Binding of Fullerene to Metal Complexes through Hydrocarbon BridgesHerrn Professor Herbert Walter Roesky zum 60. Geburtstag gewidmet.Hydrofulleride [C60H]- is added to the hydrocarbon ligands of the cationic complexes [(OC)5Re(η2-C2H4)]+, [(OC)3Mn-(η6-C6H6)]+, [(OC)3M(η5-C6H7)]+ (M = Fe, Ru), [(OC)3Fe(η5-C7H9)]+, and [(η5-C5H5)Fe(η6-C5H4CH2)]+.
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    Controlled Conversion of the Transient 2-Mesityl-1,1-bis(trimethylsilyl)silene into a Tetrahydro-2,3-disilanaphthalene, a 1,2-Disilacyclobutane, or a 1,3-Disilacyclobutane (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1083-1088 
    Details
    ISSN: 0009-2940
    Keywords: Silenes ; Silene dimerization ; 1,2-Disilacyclobutanes ; 1,3-Disilacyclobutanes ; 2,3-Disilanaphthalene, tetrahydro- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mesityl[tris(trimethylsilyl)silyl]methanol (1) reacts with strong bases with elimination of trimethylsilanolate according to a Peterson-type mechanism, the outcome of the reaction being dependent on solvent, temperature, and nature of the organometallic base applied. Thus, 1 was converted by treatment with MeLi in ether at -78°C to (E)-1,2,3,8a-tetra -hydro-1-mesityl-5,7,8a-trimethyl-2,2,3,3-tetrakis (trimethylsi-lyl)-2,3-disilanaphthalene (3), formally a [2 + 4] cyclodimer of the transient silene (Me3Si)2Si=CHMes (2). The reaction of 1 with PhMgBr in THF after some days resulted in the formation of (Z)-3,4-dimesityl-1,1,2,2-tetrakis(trimethylsilyl) -1,2-disilacyclobutane (6) as the main product besides small quantities of 3, the polysilane (Me3SiSi(SiMe3)2CH2Mes (10), and the alkoxysilane (Me3Si)3SiCH(Mes)OSi(Si-Me3)2CH2Mes (7). Compound 6, the formal [2 + 2] cycloadduct of 2, can also be obtained by thermal treatment of 3 and is considered to be the thermodynamically more stable silene dimer whereas 3 is the kinetically preferred product. At high LiBr concentrations in the reaction mixture 1 was converted by PhMgBr in THF to (E)-2,4-dimesityl-1,1,3,3-tetrakis(tri- methylsilyl)-1,3-disilacyclobutane (13) besides 6 and [bis(tri-methylsilyl)silyl]mesityl(trimethylsiloxy)methane (11). The unforeseen formation of 13 is discussed as proceeding via the silene-lithium bromide adduct (Me3Si)2Si(Br)CH(Li)Mes (12). In the absence of LiBr 1 was converted by MeLi in THF at -78°C to 11 and the trisilane (Me3Si)2Si(Me)CH2Mes (4b). Probable pathways of the formation of all new compounds are discussed. For 6 and 13 the results of the X-ray structural analyses are given.
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    Metallkomplexe mit biologisch wichtigen Lisganden, LXXXLXXIX. Mitteilung: Lit.. (η3:η3-C10H16)Ru(IV)-Komplexe mit α-Aminocarboxylaten, α-Aminosäureestern und Peptidestern als Liganden (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1117-1125 
    Details
    ISSN: 0009-2940
    Keywords: 1,7-Dimethylocta-2,6-diene-1,8-diyl ; Ruthenium complexes ; α-Amino carboxylates ; α-Amino acid esters ; Peptide esters ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metal Complexes Containing Biologically Important Ligands, LXXXLXXIX. Mitteilung: Lit. .  -  (η3:η3-C10H16)Ru(IV) Complexes with α-Amino Carboxylates, α-Amino Acid Esters, and Peptide Esters as LigandsReactions of the chloro-bridged bis(allyl) complex [(η3:η3-C10H16)Ru(Cl)(μ-Cl)]2 with α-amino carboxylates and α-amino acid esters afford the complexes (η3:η3-C10H16)(Cl)RuNH2CHRCO2 (2) and (η3:η3-C10H16)(Cl)2-RuNH2CHRCO2R′ (3). Abstraction of chloride from 3 by Ag+ gives the N,O-chelates [(η3:η3-C10H16)(Cl)RuNH2CHRCO2R′]+BF4 (4). Cysteine methyl ester forms the N,S-chelate complex (η3:η3-C10H16)(Cl)RuNH2CH(CO2CH3)CH2S (5), and with histidine methyl ester a dinuclear complex 6 with N,N-histidine bridge is obtained. Compound 3d with L-PheOEt as ligand was characterized by X-ray diffraction.
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    [MeO(CH2CH2O)3(CH2)3C5Me4]FeCl: A Halfsandwich Iron (II) Chloride Complex of Remarkable Stability (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1135-1136 
    Details
    ISSN: 0009-2940
    Keywords: Hemilabile ligands ; Cyclopentadienyl ligands, functionalised ; Iron compounds ; Halfsandwich complex ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of iron(II) chloride with one equivalent of [MeO-(CH2CH2O)3(CH2)3C5Me4]Li in THF yields the title halfsand-wich complex 1, which is stable in solution up to room temperature. Compound 1 reacts with C5H5Li and CO to give [MeO(CH2CH2O)3(CH2)3C5Me4]Fe(C5H5) (2) and [MeO-(CH2CH2O)3(CH2)3C5Me4]Fe(CO)2CI (3), respectively, in high yields.
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    [Cp4Fe4(E2)2] Clusters with Triangulated Dodecahedral Fe4E4 Skeletons (E = P, As)Dedicated to Professor Herbert Schumann on the occasion of his 60th birthday. (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1145-1148 
    Details
    ISSN: 0009-2940
    Keywords: P2, As2, P2S2, and P2Se2 ligands ; Iron complexes ; Triangulated dodecahedra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermolysis of [CpFe(CO)2]2 (1) and P4 or As4 affords the iron clusters [Cp4Fe4(E2)2], E = As (2a), P (2b), the Fe4E4 skeleton of which consists of a triangulated dodecahedron. S8 and gray Se oxidize the P2 ligands of 2b with formation of [Cp4Fe4(P2X2)2], X = S (3a), Se (3b), complexes with the hitherto unknown P2X2 ligands, 2a, b and 3a, b have been characterized by X-ray crystallography.
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    URL: http://dx.doi.org/10.1002/cber.19951281202
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    Functionalized Diorganozinc Compounds: Key Reagents for the Synthesis of Enantiomerically Pure 2,5-Disubstituted cis- and trans-Tetrahydrofurans (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1021-1028 
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    ISSN: 0009-2940
    Keywords: Synthesis, stereoselective ; Catalysis ; Tetrahydrofurans ; Dialkylzinc reagents ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,4-Diol derivatives 4a-i were synthesized stereoselectively by either reagent- or catalyst-controlled routes using the addition of functionalized diorganozinc reagents to aldehydes. The stereoselectivities along the reagent-controlled synthetic path were in the range between 80:20 and 95:5. The stereoselectivities along the catalyst route exceeded 95:5. The 1,4-diol derivatives 4 thus obtained were transformed into enantiomerically pure cis- and trans-2,5-disubstituted tetrahydrofurans (16-20) by means of an intramolecular Williamson reaction.
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    Contributions to the Chemistry of Boron, 231Part 230: Ref.. Synthesis and Structures of Borylated HydrazinesDedicated to Professor H. P. Fritz on the occasion of his 65th birthday. (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1187-1194 
    Details
    ISSN: 0009-2940
    Keywords: Hydrazines ; N,N'-bis(diphenylboryl)-N,N'-dimethyl- ; N,N'-bis(diphenylboryl)-N',N'-dimethyl- ; N,N'-bis(dimethylphenylsilyl)- ; N,N'-bis(chloromesitylboryl)-N'-phenyl-N'-(trimethylsilyl)- ; 1,2,4,5,3,6-Tetrazadiborinane, 1,2,4,5-tetrakis(tert-butyldimethylsilyl)-3,6-difluoro- ; Triazadiborolidine, dihydro-, derivative ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The diboration of the diazene PhN = NSiMe3 (15) by diborane(4) derivatives provides a new synthetic route to N,N'-diborylated hydrazines. The product formed depends on the type of the diborane(4) compound. Thus, addition of dimesityldiboron dichloride to 15 in a 1:1 ratio afforded (mesCIB)PhN-N(SiMe3)(BClmes) (16) while bis(dimethyl-amino)diboron dichloride was found to react in a 1:2 ratio to give a triazadiborolidine derivative 17. In addition, it was demonstrated that in the solid state Me2N-N(BPh2)2 (8) is a derivative of a three-membered dihydroazadiboriridine C while its isomer, (Ph2B)MeN-NMe(BPh2) (7), forms no BN coordinative bond. The new 3,6-difluoro-1,2,4,5-tetraza-3,6-diborine 13 shows a twist conformation. The molecular structures of all these compounds were determined by X-ray crystal structure analysis, and the influence of the B substituent on the conformation is discussed.
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    URL: http://dx.doi.org/10.1002/cber.19951281209
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    Metal Complexes of Functional Isocyanides, XXV. Amino(hydrazino)carbene Complexes (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1061-1068 
    Details
    ISSN: 0009-2940
    Keywords: N-Isocyanides ; N-Isocyanodialkylamine complexes ; Carbene complexes ; Imaging-Plate data collection ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The N-isocyanodialkylamine metal complexes [M(CO)5CN-NR2] (M = Cr, W), trans-[MI2(CNNR2)2] (M = Pd, Pt), trans-[Pt(Cl)(CNNR2)(PPh3)2]BF4, and cis-[PtCl2(CNNR2)(PPh3)] [R = Et, iPr; 2 R = -{CHMe(CH2)3CHMe}-] react with primary amines to give the amino(hydrazino)carbene metal complexes [M(CO)5(C(NHR′)NHNR2}] (R′ = Me, nPr, Cy) (1-9), trans-[PtI2{C(NHMe)NHNR2}2] (10-12) and trans, and the amine adducts cis-[PtCl2{C(NHMe)NHNC(H)(Me) (CH2)3CHMe}(PPh3)] H2NMe (14), and trans-[PdI2{C (NHMe)NHNC(H)(Me)(CH2)3CHMe}2] 2 H2NMe (15). With secondary amines the amino(hydrazino)carbene metal complexes trans (18) and trans-[PtCl{C(NEt2)NHNEt2} (PPh3)2]BF4 (19) Were isolated. The complexes trans-[PtI2{C(NHCy)NHNiPr2}CNNiPr 2] (20) and trans-[PdI2 (NH2Cy){C(NHCy)NHNiPr2}] (21) were obtained by reaction of trans-[MI2(CNNiPr2)2] (M = Pd, Pt) with cyclohexylamine. The structures were assigned on the basis of IR, NMR- (1H, 13C, 31P), and mass spectroscopy as well as an X-ray structural analysis of 21.
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    Metallocenophanes, VIIPart VI: Ref.. Preparation and Characterisation of the Disilver(I) Complexes of Conjugated Polyenes with [2.2.2]Paracyclophanyl End Groups (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1079-1082 
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    ISSN: 0009-2940
    Keywords: [2.2.2]Paracyclophanes ; Polyenes ; Silver complexes ; X-Ray structural analysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation of the disilver(I) complexes 3 and 4, polyene metal complexes that are terminally substituted with [2.2.2]paracyclophanyl units, is described. NMR spectro-scopic studies on the disilver perchlorate complex 3b showed that (a) the sites of complexation are the cyclophane groups and (b) the olefinic spacers do not overly perturb the overall complexation properties of the individual [2.2.2]paracyclo-phanyl groups. The crystal structures of the disilver hexafluo-roantimonate complexes 4a-b were determined. The use of the hexafluoroantimonate counterion and solvent mixtures containing toluene both proved crucial in obtaining single crystals; toluene is incorportated into the crystal lattices.
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    Highly Substituted Tris(pyrazolyl)methane Ligands and Some Zinc Complexes Thereof (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1095-1103 
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    ISSN: 0009-2940
    Keywords: Zinc complexes ; Tridentate ligands ; Tris(pyrazolyl)methane ; Reactivity ; Structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tris(pyrazolyl)methane ligands in which two or three of the pyrazole carbon atoms bear organic substituents (L1-L7) were synthesized from chloroform and the corresponding pyrazole under phase transfer conditions. Their behavior towards zinc salts was found to span the range from no reaction at all to hydrolytic destruction. One hydrolysis product isolated and structurally characterized was the perchlorate complex [(HPz5)3Zn-OClO3]ClO4 (1), other ones were the 2:1 complexes (HPz3)2ZnBr2 (2) and (HPz6)2Zn(NO3)2 (3, HPzn = substituted pyrazole). Zinc perchlorate and tris(trimethylpy-razolyl)methane (L2) formed the octahedral binary complex [L22Zn](ClO4)2 (4) as evidenced by a structure determination. Zinc halides produced the 1:1 complexes L1 · ZnBr2 (5), L4 · ZnCl2 (6), and L4 · ZnBr2 (7), which according to the structure determinations of 6 and 7 contain tetrahedral ZnN2Hal2 units with only bidentate tris(pyrazolyl)methane ligands. In contrast, the zinc nitrate complex L4 · Zn(NO3)2 (8) was found to have an octahedral structure with mono- and bidentate nitrate and tridentate L4. The bromide complex 7 was converted by silver perchlorate hydrate into the labile compound [L4 · ZnBr]ClO4 (9) and then into the unstable product [L4 · Zn-OH2](ClO4)2 (10), both presumed to contain zinc in a tetrahedral ZnN3Br or ZnN3O environment, respectively. The ease of hydrolytic self-destruction prevented the exploitation of the reactivity of 9 and 10 in analogy to that of the corresponding tris(pyrazolyl)borate zinc complexes.
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    Unusual Complexation Behavior of Metallomacrocycles Based on Isothiosemicarbazides with Respect to Alkali and Alkaline Earth Metal Ions: Novel 2:1 Associates (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1089-1093 
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    ISSN: 0009-2940
    Keywords: Metallomacrocycles ; Nickel complexes ; Complexation reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions between alkali and alkaline earth metal ions and nickel(II) macrocycles based on S-alkylated isothiosemi-carbazides with different crown ether cavity size were studied in propylene carbonate by spectrophotometric and calorimetric titrations. Metallomacrocycles 1 and 2 exhibit normal behavior on 1:1 complexation with alkali- and alkaline earth metal ions and resemble in this respect 15C5 and 18C6, respectively. The most stable complexes are formed by these “ligands” when the diameter of the cation and the crown ether hole have approximately the same size. The most striking feature of the complexation processes studied is the formation of 1:2 metal-ligand associates even in the case of the smallest cations. These associates are very different from “normal” crown ether sandwich complexes. In reality, the particle formed is an associate between a 1:1 complex, in which the corresponding metal ion is well accommdated inside the ligand cavity, and a second metallomacrocyclic ligand. Their formation is disfavored by enthalpic contributions. A special kind of “switch” from these associates to normal sandwich complexes takes place in the case of 1, when the cation diameter compared to hole size increases. The macrocycle 2 forms this kind of associates with all akali and alkaline earth ions.
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    Synthesis and Reactivity of Silicon Transition Metal Complexes, 3433. Mitteilung: Lit.. Pentachlordisilanyl- und Disilanyl-Komplexe von Molybdän und Wolfram: Darstellung, Struktur und spektroskopische CharakterisierungHerrn Professor Hubert Schmidbaur zum 60. Geburtstag gewidmet. (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1109-1115 
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    ISSN: 0009-2940
    Keywords: Silicon transition metal complexes ; Metallodisilanes ; Nucleophilic metallation ; Cl/H exchange at silicon ; Raman spectroscopy ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Reactivity of Silicon Transition Metal Complexes, 34[*].  -  Pentachlorodisilanyl and Disilanyl Complexes of Molybdenum and Tungsten: Synthesis, Structure, and Spectroscopic CharacterizationReaction of the lithium metallates Li[M(PMe3)(CO)2C5R5] [M = Mo, W; R = H (1a, b), Me (1c, d)] with Si2Cl6 (2) leads to the formation of the pentachloro(metallo)disilanes 5R5(OC)2(Me3P)M - SiCl2 - SiCl3 (3a - d), which are transformed into the metallo disilanes C5R5(OC)2(Me3P)M - SiH2 - SiH3 (4a - d) on treatment with LiAlH4. The disilanes 4a - d are reconverted into 3a - d in the presence of tetrachloromethane. Extensive spectroscopic investigations (NMR, Raman, and IR spectroscopy) were performed to establish the transition-metal effect especially with respect to the H5Si2 ligand. The molecular structure of C5Me5(OC)2(Me3P)W - SiCl2 - SiCl3 (3d) was determined by single-crystal X-ray diffraction.
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    Octacarbonylbis {μ-(tris(trimethylsilyl)methyl]indany l} dimanganese with Two Monoalkyl Indium Groups Bridging the Mn-Mn Bond (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1137-1139 
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    ISSN: 0009-2940
    Keywords: Tetraindane(4) ; Indium(I) ; Mn-Mn bond ; Indium alkyl bridge ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetrahedra-tetrakis[tris(trimethylsilyl)methyl]tetraindane(4) (1) reacts with decacarbonyldimanganese(0) to yield the bright red crystalline title compound 2, in which two carbonyl ligands are replaced by two InR fragments. The crystal structure determination of 2 shows two Mn(CO)4 groups (Mn-Mn 313.7 pm) bridged by two monoalkylindium units and a planar Mn2In2 molecular center.
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    Thioselonocarboxylic Ester, Selenetane, and Dihydrodiselenine Complexes Prepared from Pentacarbonyl(selenobenzaldehyde)tungsten with π-Donor-Substituted Alkynes (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1149-1156 
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    ISSN: 0009-2940
    Keywords: Selenoaldehyde complex ; Thioselonocarboxylic ester complexes ; Selenetane complex ; Dihydrodiselenine complex ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pentacarbonyltungsten-coordinated selenobenzaldehyde, [(CO)5W{Se=C(Ph)H}] (1), reacts with tBu-C≡C-SMe (2) by insertion of the C≡C into the Se=C bond to form in a highly regio- and stereoselective manner the α,β-unsaturated thioselonocarboxylic ester complex (Z)(C=C)-[(CO)5W{≡1-Se=C(SMe)C(tBu)=C(Ph)H}] (3). The thioselonocarboxylic ester ligand is cleaved intact from the metal by treatment of 3 with [NEt4]Br. Three complexes are formed in the reaction of 1 with Me-C≡C-SMe (5): the thioselonocarboxylic ester complex [(CO)5W{≡1-Se=C(SMe)C(Me)=C(Ph)H}] (6) as a mixture of the (E) and (Z)(C=C) isomers, a selenetane complex (7) and a dihydrodiselenine complex (8). The product distribution depends on the ratio 1:5 and on the solvent. The reaction of 1 with the bis(organylthio)alkynes RS-C≡C-SR (9) [R = Me (a), iPr (b), 2,6-C6H3Me2 (c)] yields mixtures of the (E) and (Z)(C=C) isomers of the α,β-unsaturated α-organylthio thioselonocarboxylic ester complexes [(CO)5W{≡1-Se=C(SR)C(SR)=C(Ph)H)] (10a-c). In contrast, the reaction of 1 with tert-butoxyethyne, H-C≡C-OtBu (11), affords a bis(pentacarbonyltungsten) 5,6-dihydro-1,2-diselenine complex (12). Compound 12 is probably formed by consecutive reaction of 1 with 11 to give the selonocarboxylic ester complex [(CO)5W{≡1-Se=C(OtBu)C(H)=C(Ph)H}] which then further reacts as a heterodiene by highly regioselective [4 + 2] cycloaddition with the Se=C bond of a second molecule of 1 to give 12. In the reaction of 1 with 5 and 9a the isomer with a trans arrangement of C(=Se)SMe and Ph is the kinetically controlled reaction product [(E)-6 and (Z)-10a, respectively]. The formation of (E)-6 and (Z)-10a is followed by isomerization until an (E)/(Z) equilibrium is reached. Complexes 3 and 7 were characterized by X-ray structural analyses.
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    Tin for Organic Synthesis, 13Part 12: Ref.. A New and Regioselective Method for the Synthesis of Aromatic, Heteroaromatic, and Olefinic Sulfonamides by Electrophilic Destannylation (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1195-1198 
    Details
    ISSN: 0009-2940
    Keywords: Electrophilic aromatic substitution ; Electrophilic vinylic substitution ; Trialkylstannanes, application of ; Sulfonamides, synthesis of ; Sulfodestannylation, application of ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A mild and effective method for the preparation of aromatic and olefinic sulfonamides is described. The reaction of trialkylaryl- (4a-f), heteroaryl- (4g), and vinylic stannanes (4h) with sulfuryl chloride and secondary amines provides the corresponding sulfonamides in an ipso-specific manner.
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    Ylidylphosphorsulfide, -selenide, -disulfide, -sulfidselenide und -diselenide (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1207-1219 
    Details
    ISSN: 0009-2940
    Keywords: Ylide-substituted phosphorus ; Phosphorus sulfides ; Phosphorus selenides ; Thioxophosphanes ; Selenoxo-phosphanes ; Dithioxophosphoranes ; Diselenoxophosphoranes ; Alkylation reactions ; Selenadiphosphirane ; 2,5,7-Triselena-1,3,4,6-tetraphosphanorbornane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ylidylphosphorus Sulfides, Selenides, Disulfides, Sulfide Selenides, and DiselenidesWe report on the first stable monomeric phosphorus mono-chalcogenides 2, 8 and the first stable dichalcogenides 4, 10 without bulky or intramolecularly coordinating substituents. They are stabilized by a high contribution of the zwitterionic resonance formula, which follows both from the NMR spectra and from an X-ray structure determination. Their preparation starts from triphenylphosphoniumylidyl-dichlorophosphanes 1. For the monochalcogenides they are treated with sodium sulfide or selenide or better with bis(trimethylsilyl) sulfide or selenide. In case of the C-phenyl and C-meta-tolyl representatives and also of the C-trimethylsilyl compound a number of secondary, partly novel products are obtained. - The dichalcogenides result from the reaction with sodium disulfide and diselenide, respectively, or from the oxidation of the monochalcogenides. - Alkylation of the monochalcogenides results in ylidylalkylchalcogenophosphenium salts 13, 15. In solution they are in equilibrium with more or less of the covalent form 14, 16, depending on the anion and on the solvent. Alkylation is often accompanied by secondary reactions. A diselenide loses selenium on alkylation.
    Additional Material: 3 Ill.
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    Synthesis and Reactivity of Silicon Transition Metal Complexes, 3332. Mitteilung: Lit.. Metallo Silanols and Metallo Siloxanes, 87. Mitteilung: Lit.. Metallo-silanole vom Typ C5R5(OC)2(Me3P)M - SiPh2OH (M = Cr, Mo, W): Darstellung nach der Dimethyldioxiran-Methode und Überführung in funktionalisierte Metallo-disiloxaneHerrn Professor Max Schmidt zum 70. Geburtstag gewidmet. (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1251-1255 
    Details
    ISSN: 0009-2940
    Keywords: Oxofunctionalization ; Dimethyldioxirane ; Metallo silanes ; Metallo silanols ; Metallo siloxanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis and Reactivity of Silicon Transition Metal Complexes, 3332. Mitteilung: Lit. .  -  Metallo Silanols and Metallo Siloxanes, 8 7. Mitteilung: Lit. .  -  Metallo Silanols of the Type C5R5(OC)2(Me3P)M-SiPh2OH (M = Cr, Mo, W): Preparation According to the Dimethyldioxirane Route and Conversion into Metallo Disiloxanes Herrn Professor Max Schmidt zum 70. Geburtstag gewidmet.The metallo silanes C5R5(OC)2(Me3P)M-SiPh2H (4a-c), are converted into the corresponding metallo silanols C5R5(OC)2-(Me3P)M-SiPh2OH [R = H, M = Cr (6a); R = Me, M = Mo (6b); M = W (6c)] by oxofunctionalization with dimethyldioxirane (5). Treatment of 6b, c with the chlorosilanes Me2Si(R)Cl [R = H (3b), [R = Cl (3c)] in the presence of triethylamine gives access to the metallo disiloxanes C5Me5(OC)2(Me3P)M-SiPh2OSiMe2R (M = Mo, R = H (7a); M = W, R = Cl (7b)]. The structure of tungsten silanol 6c is determined by X-ray diffraction analysis.
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    URL: http://dx.doi.org/10.1002/cber.19951281217
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    Synthesis and Characterization of β-Phosphaenones An Investigation on the Conjugative Properties of the P=C Bond (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 465-476 
    Details
    ISSN: 0009-2940
    Keywords: Phosphaalkenes, C-halo, C-metal ; Phosphaacrylic acid ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermally and air-stable β-phosphaenones were synthesized by functionalization of Mes*P=CCl2 (1; Mes* = supermesityl = 2,4,6-tri-tert-butylphenyl). At low temperature, 1 was lithiated by halogen-metal exchange with n-butyllithium to give the phosphanylidene carbenoid (Z)-Mes*P=C(Cl)Li [(Z)-2] which reacted with acid chlorides to furnish the C-carbonyl-substituted phosphaalkenes (Z)-Mes*P=C(Cl)R (3: P = COtBu; 4: R = COPh; 5: R = COOEt). The reaction of (Z)-2 with carbon dioxide furnished the carboxylate 6, which was converted by treatment with pivaloyl chloride or trimethylsilyl chloride into the phosphaalkenes 7 and 8 functionalized at the carbon atom by an anhydride or a trimethylsilyl ester function, respectively. Acidification of 6 or hydrolysis of 8 with water in chloroform solution afforded the novel carboxylic acid (Z)-Mes*P=C(Cl)COOH (9). Spectroscopic investigations (NMR, UV, IR) of 3-9 and the X-ray structures of 3 and 4 are presented. Based on these properties and on theoretical calculations, the occurrence of conjugation in the β-phosphaenone system is discussed and compared with the well-known conjugation in normal enones.
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    Reactions of Phosphaalkenes with HexafluoroacetoneDedicated to Professor H. M. R. Hoffmann on the occasion of his 60th birthday. (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 499-502 
    Details
    ISSN: 0009-2940
    Keywords: Phosphaalkenes ; Cycloadditions ; Insertion reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dimethylamino-substituted phosphaalkene 1 reacts with hexafluoroacetone (HFA) with addition at the P=C bond to form the 1,5,2-dioxaphosphorinane 2. The structure of 2 was confirmed by an X-ray crystal structure analysis. The six-membered ring displays an envelope conformation with the phosphorus atom out of the plane, but the phosphorus is disordered over two sites. Reaction of P-trimethylsilyl-substituted phosphaalkenes with HFA proceeds with retention of the P=C double bond and insertion of HFA into the P—Si bond. Two isomeric products are obtained and are characterized by 1H-, 13C-, 19F-, and 31P-NMR spectroscopy, IR spectroscopy, mass spectrometry, and elemental analysis.
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    Monomere (Acetylacetonato)kupfer(I)-Komplexe von Alkinen und 1,4-Diinen (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 525-529 
    Details
    ISSN: 0009-2940
    Keywords: Copper complexes ; Acetylacetonate ; Alkynes ; 1,4-Diynes ; Titanocenes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monomeric (Acetylacetonato)copper(I) Complexes of Alkynes and 1,4-DiynesMonomeric (η2-Me3SiC≡CSiMe3)Cu(acac) (3) is formed by the reaction of dimeric [(η2-Me3SiC≡CSiMe3)CuBr]2 (1) with two equivalents of Na(acac) (2). In a similar manner Me2-Si(C≡CSiMe3)2 (4) reacts with CuCl (5) and 2 to afford Me2Si[(η2-C≡CSiMe3)Cu(acac)]2 (6). In compounds 3 and 6 an alkyne unit is η2-coordinated to a monomeric Cu(acac) moiety with a copper atom in a planar environment. With the organometallic 1,4-diyne (η5-C5H4SiMe3)2Ti(C≡CSiMe3)2 (7), compound [(η5-C5H4SiMe3)2Ti(C≡CSiMe3)2]Cu(acac) (8) is formed. In 8 both Me3SiC≡C ligands of the 3-titanapenta-1,4-diyne fragment are η2-coordinated to a monomeric Cu-(acac) building block. The copper atom in 8 possesses a pseudo-tetrahedral environment (shown by X-ray analysis), built by the two Me3SiC≡C ligands of the (η5-C5H4SiMe3)2-Ti(C≡CSiMe3)2 moiety and the two oxygen atoms of the acetylacetonato ligand. 8 is additionally formed by the reaction of 3 or 6 with 7, or by treatment of [(η5-C5H4SiMe3)2Ti(C≡C-SiMe3)2]CuCl (9) with Na(acac) (2). The application of 3, 6, and 8 as precursors for the preparation of copper films in the CVD process of copper(I) is discussed.
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    Chiral Organometallic Reagents, XIIIPart XII: Ref.. Structural Aspects of Differentially Solvated Benzyllithium Contact Ion Pairs (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 551-556 
    Details
    ISSN: 0009-2940
    Keywords: Benzyllithium compounds ; Ion pairs ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solvation and ion pair nature of α-(phenylthio)benzyllithium (2d) in THF solution were investigated by NMR-spectroscopic methods. The effect of additives such as diethylene-glycol dimethyl ether or of 12-crown-4 was studied. The results were compared to those of benzyllithium compounds 4 and 6, containing a pentaoxapentadecane ansa chain. These compounds exist as contact ion pairs in which lithium is held at the anionic carbon. This is reflected in the 6Li,13C coupling and 1H,6Li-HOESY contacts in the NMR spectra.
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    URL: http://dx.doi.org/10.1002/cber.19951280604
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    Sulfur Compounds, Part 186Part 185: K. Bergemann, M. Kustos, P. Krüger, R. Steudel, Angew. Chem., in print.. The Synthesis of Cyclic Organosulfur Compounds from (C5H5)4Ti2C2S4 by Ligand Transfer Reactions (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 561-564 
    Details
    ISSN: 0009-2940
    Keywords: Titanocene complexes ; Organosulfur ligands ; Ligand transfer ; Organosulfur heterocycles ; Sulfur-sulfur bonds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tetrathiaoxalate complex Cp4Ti2C2S4 (1) reacts with an equimolar amount of COCl2 to give the blue-green mononuclear complex Cp2TiC2S4CO (4). This reaction is analogous to the known reactions of 1 with SCl2 or S2Cl2. However, when 1 was treated with equimolar amounts of the bifunctional sulfenyl chlorides 1,2-C2H4(SCl)2 (5), 1,3-C3H6(SCl)2 (6) or 1,2-C6H4(SCl)2 (7), the bi- or monocyclic tetrakisdisulfanes C6H8S8 (9b), C8H12S8 (10), and C14H8S8 (11), respectively, were obtained. The X-ray crystal structure analysis of 11 · CS2 showed that 11 possesses Ci symmetry with a central exocyclic CC double bond similar to tetrathiafulvalenes: C6H4(μ-S2)2C=C(μ-S2)2C6H4.
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    Norbornadiene(bipyridyl)molybdenum(II) Complexes: Synthesis, Structure and Reactivity of [Mo(CO)(C7H8)(C10H6R2N2)X2] (X = I, Br)Dedicated to Professor Dr. Helmut Werner on the occasion of his birthday. (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1007-1013 
    Details
    ISSN: 0009-2940
    Keywords: Tetracarbonyl(norbornadiene)molybdenum(0) ; Oxidative addition of I2 ; Dihalogeno(bipyridyl)molybdenum(II) complexes ; 7-Coordinated complexes ; Neutral and cationic molybdenum(II) complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of [Mo(CO)4(C7H8)] (1) with I2 gave the norbornadienemolybdenum(II) complex [Mo(CO)2(C7H8)I2]n≥1 (2), which existed in an equilibrium of two isomeric forms. In acetonitrile, 2 reversibly formed the adduct [Mo(CO)2-(C7H8)(NCCH3)I2] (3), whereas on treatment with 2,2′-bipyridine or 4,4′-di-2,2′-tBu-bipyridine, it gave stable 7-coordinated molybdenum(II) complexes, [Mo(CO)(C7H8)-(C10H8N2)I2] (4) and [Mo(CO)(C7H8)(C10H6tBu2N2)I2] (5), in good yield. In similar reactions, the related dibromomolybdenum compounds [Mo(CO)(C7H8)(C10H8N2)Br2] (6) and [Mo-(CO)(C7H8)(C10H6tBu2N2)Br2] (7) were prepared by oxidation of 1 with two equivalents of CuBr2. The X-ray structural analysis of 6 reveals that the geometry around the molybdenum atom is nearly perfectly pentagonal bipyramidal, with the CO and one of the bipyridyl rings perpendicular to the plane formed by the other ligands. The compounds 5 and 6 react with AgSbF6 by halogen abstraction to give cationic complexes, {[Mo(CO)(C7H8)(C10H8N2)Br]SbF6}n≥1 (8) and {[Mo(CO)(C7H8)(C10H6tBu2N2)I]SbF6}n≥1 (9): In acetone, 8 and 9 reversibly formed the adducts [Mo(CO)(C7H8)(C10H8N2)(acetone)Br]SbF6 (8′) and [Mo(CO)(C7H8)(C10H6tBu2N2)(acetone)I]SbF6 (9′); while on treatment with PMe3, the stable monomeric complexes, [Mo(CO)(C7H8)(C10H8N2)(PMe3)Br]SbF6 (10) and [Mo(CO)(C7H8)(C10H6tBu2N2)(PMe3)I]SbF6 (11), were isolated in almost quantitative yield. In the presence of KBr, compound 8′ reverted to the dibromo complex 6, whereas 9′ reacted to produce a 1:1:2 mixture of 5, 7 and the bromo(iodo) complex [Mo(CO)(C7H8)(C10H6tBu2N2)BrI] (12). The same mixture is available from the reaction of 5 with one equivalent of 7.
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    Graphical Abstract (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. A149 
    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.19951281018
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    Amino Substituted Tricarbonyl(cyclobutadiene)iron Complexes: Pd-Catalyzed Coupling of Iodocyclobutadiene Complexes with Amines (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1055-1058 
    Details
    ISSN: 0009-2940
    Keywords: Aminations ; Palladium catalysis ; Organometallic amines ; Coupling reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The coupling of the iodides 1 with amines under palladium catalysis affords the novel aminated cyclobutadiene derivatives 2 in preparative useful yields.
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    URL: http://dx.doi.org/10.1002/cber.19951281016
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    Masthead (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951281101
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    Chiral Carbanions, 1. Configurational Stability and Reactions of α-Acyloxy-Substituted α-Methylbenzyllithium Compounds (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1069-1077 
    Details
    ISSN: 0009-2940
    Keywords: Esters, 1-phenylethyl ; Carbanions, α-methyl-α-oxybenzyl, Configurational stability ; Ester - hydroxy ketone rearrangement ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Racemic and optically active 1-phenylethyl esters of pivalic, ( - )-camphanic and 2,4,6-triisopropylbenzoic acid were prepared. The esters 7a of pivalic acid were deprotonated with lithium 2,2,6,6-tetramethylpiperidide (Li-TMP) to form α-oxy-α-methylbenzyllithium compounds which are partly con-figurationally stable prior to acylation with starting material. Camphanic ester (-)-7b cannot be deprotonated by Li-TMP and tBuLi is added to the ester function to afford ketone (-)-12a. 1-Phenylethyl 2,4,6-triisopropylbenzoates 16 were transformed within minutes to carbanions 19 by using sBuLi/TMEDA in THF, hexane, toluene and sBuLi without TMEDA in toluene/20% diethyl ether at -78°C. The carbanions are configurationally stable only in toluene/20% diethyl ether and racemise partly in the other solvents. They react with a variety of electrophiles with either retention [MeOD, AcOD, (MeO)2CO, CICO2Me] or inversion (Me3SnCl) of configuration. Carbanions 19 rearrange on warming to -20°C to hydroxy ketone 24 with racemisation.
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    URL: http://dx.doi.org/10.1002/cber.19951281103
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