ALBERT

All Library Books, journals and Electronic Records Telegrafenberg

X
feed icon rss

Your email was sent successfully. Check your inbox.

An error occurred while sending the email. Please try again.

Proceed reservation?

Export
Filter
  • Chemistry  (407,117)
  • stability
  • Wiley-Blackwell  (407,112)
  • Springer  (715)
  • MDPI Publishing
Collection
Keywords
Publisher
Years
  • 1
    facet.materialart.
    Unknown
    Editorial: Flank dynamics, sector collapses, lahars, and rockfalls: analysis, monitoring, and modelling of small to large scale volcanic slope instability (2020)
    Springer
    Details
    Publication Date: 2020-11-12
    Description: Slope dynamics in volcanic environments comprise a wide spectrum of phenomena, from large lateral collapse to shallow debris remobilization, which may represent a major threat for human communities and infrastructures. Many volcanos built up from the ocean floor and large portions of the volcano edifice are submerged. In these settings, only the edifice’s summit can be investigated by terrestrial remote sensing and in-situ approaches. Growth and destruction, including tectonics and gravitational phenomena, affect entire volcano flanks and are not limited to the physical boundary of the sea level but could comprise their subaqueous parts.
    Description: Published
    Description: 2615–2618
    Description: 6V. Pericolosità vulcanica e contributi alla stima del rischio
    Description: JCR Journal
    Keywords: volcanoes ; flanks ; volcano-tectonics ; structure ; collapse ; stability ; 04.08. Volcanology ; 05.08. Risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    PAPER (OA)
  • 2
    Electronic Resource
    Electronic Resource
    The consequences of the mutual recognition of measurement standards for international metrology (2000)
    Springer
    Accreditation and quality assurance 5 (2000), S. 409-413 
    Details
    ISSN: 1432-0517
    Keywords: Key words Metrology ; Comparisons ; Chemistry ; Standards
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract  After stressing the importance in the modern world of accurate and reproducible measurements, the actions taken by the Bureau International des Poids et Mesures to set up, together with the regional metrology organizations, a series of key comparisons are described. They are the technical foundation of a mutual recognition of national measurement standards arrangement prepared in conjunction with the National Metrology Institutes (NMIs). This arrangement also includes the recognition of calibration and measurement certificates issued by these institutes. Then, the consequences of this arrangement for trade are described. The case of chemical analysis is illustrated by the application of the Kyoto protocol on the reduction of greenhouse gases. But the global workload to be taken up by the International Committee of Weights and Measures, its Consultative Committee for Amount of Substance and the NMIs is huge.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s007690000228
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 3
    Electronic Resource
    Electronic Resource
    Surface Instability of Laminated Coatings upon Inelastic Deformation (2000)
    Springer
    Mechanics of composite materials 36 (2000), S. 475-480 
    Details
    ISSN: 1573-8922
    Keywords: stability ; three-dimensional theory ; tribotechnics ; elastoplastic deformations ; viscoelasticity ; surface ; tracking and dead loads ; laminated coating ; piecewise-homogeneous model ; active loading
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The problem of surface instability of laminated coatings with inelastic properties is considered within the framework of a model of piecewise-homogeneous media on the basis of the three-dimensional linearized theory of stability. A general statement of the problem is formulated and the basic characteristic equations are derived. The solutions of particular problems are obtained for elastoplastic and viscoelastic models of solids.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1006758600457
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 4
    Electronic Resource
    Electronic Resource
    On the Stability of Nonconservative Systems with Estimation of the Attraction Domain (2000)
    Springer
    Journal of dynamical and control systems 6 (2000), S. 503-510 
    Details
    ISSN: 1573-8698
    Keywords: nonconservative mechanical systems ; stability ; Lyapunov functions ; attraction domain
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Mechanical systems subjected to dissipative, gyroscopic, conservative, and also nonconservative positional forces are considered. The question of the effect of dissipative, gyroscopic, and conservative forces on the motion stability of a mechanical systems is determined by classical Kelvin–Chetaev theorems [1]. The presence of nonconservative positional forces considerably complicates the situation and excludes direct application of these theorems. Applying Lyapunov's functions method the condition of asymptotic stability of a mechanical system under the action of all listed above forces is obtained. Moreover, the estimation of the attraction domain in phase space is found. The precession system which is used in the solution of some problems in the applied theory of the gyroscopic systems is also examined. The connection between the stability of origin and precession systems is detected. Theoretical results are applied to the stabilization problem of stationary motion of the balanced gimbal suspension gyro by means of external moments.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1009500527061
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 5
    Electronic Resource
    Electronic Resource
    Stability of Solutions of Stochastic Functional Differential Equations with an Infinite Previous History and Poisson Switchings. II (2000)
    Springer
    Cybernetics and systems analysis 36 (2000), S. 699-721 
    Details
    ISSN: 1573-8337
    Keywords: stability ; stochastic functional differential equations ; previous history ; Poisson switchings ; "dangling spider" model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science
    Notes: Abstract To study the stability of the stochastic "dangling spider" model, the second Lyapunov method is substantiated for stochastic differential functional equations with the whole previous history.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1009428806622
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 6
    Electronic Resource
    Electronic Resource
    Protein Spray-Freeze Drying. Effect of Atomization Conditions on Particle Size and Stability (2000)
    Springer
    Pharmaceutical research 17 (2000), S. 1374-1382 
    Details
    ISSN: 1573-904X
    Keywords: particle size ; PLG microspheres ; protein delivery ; spray-freeze drying ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. To investigate the effect of atomization conditions on particle size and stability of spray-freeze dried protein. Methods. Atomization variables were explored for excipient-free (no zinc added) and zinc-complexed bovine serum albumin (BSA). Particle size was measured by laser diffraction light scattering following sonication in organic solvent containing poly(lactide-co-glycolide) (PLG). Powder surface area was determined from the N2 vapor sorption isotherm. Size-exclusion chromatography (SEC) was used to assess decrease in percent protein monomer. Fourier-transform infrared (FTIR) spectroscopy was employed to estimate protein secondary structure. PLG microspheres were made using a non-aqueous, cryogenic process and release of spray-freeze dried BSA was assessed in vitro. Results. The most significant atomization parameter affecting particle size was the mass flow ratio (mass of atomization N2 relative to that for liquid feed). Particle size was inversely related to specific surface area and the amount of protein aggregates formed. Zinc-complexation reduced the specific surface area and stabilized the protein against aggregation. FTIR data indicated perturbations in secondary structure upon spray-freeze drying for both excipient-free and zinc-complexed protein. Conclusions. Upon sonication, spray-freeze dried protein powders exhibited friability, or susceptibility towards disintegration. For excipient-free protein, conditions where the mass flow ratio was 〉 ∼0.3 yielded sub-micron powders with relatively large specific surface areas. Reduced particle size was also linked to a decrease in the percentage of protein monomer upon drying. This effect was ameliorated by zinc-complexation, via a mechanism involving reduction in specific surface area of the powder rather than stabilization of secondary structure. Reduction of protein particle size was beneficial in reducing the initial release (burst) of the protein encapsulated in PLG microspheres.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1007570030368
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 7
    Electronic Resource
    Electronic Resource
    Formulation Development and Antitumor Activity of a Filter-Sterilizable Emulsion of Paclitaxel (2000)
    Springer
    Pharmaceutical research 17 (2000), S. 175-182 
    Details
    ISSN: 1573-904X
    Keywords: paclitaxel ; emulsions ; filter-sterization ; particle size ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. Paclitaxel is currently administered i.v. as a slow infusion of asolution of the drug in an ethanol:surfactant:saline admixture. However,poor solubilization and toxicity are associated with this drug therapy.Alternative drug delivery systems, including parenteral emulsions, areunder development in recent years to reduce drug toxicity, improveefficacy and eliminate premedication. Methods. Paclitaxel emulsions were prepared by high-shearhomogenization. The particle size of the emulsions was measured by dynamiclight scattering. Drug concentration was quantified by HPLC and invitro drug release was monitored by membrane dialysis. The physicalstability of emulsions was monitored by particle size changes in boththe mean droplet diameter and 99% cumulative distribution. Paclitaxelpotency and changes in the concentration of known degradants wereused as chemical stability indicators. Single dose acute toxicity studieswere conducted in healthy mice and efficacy studies in B16 melanomatumor-bearing mice. Results. QW8184, a physically and chemically stable sub-micronoil-in-water (o/w) emulsion of paclitaxel, can be prepared at high drugloading (8-10 mg/mL) having a mean droplet diameter of 〈100 nmand 99% cumulative particle size distribution of 〈200 nm. In vitro release studies demonstrated low and sustained drug release both inthe presence and absence of human serum albumin. Based on singledose acute toxicity studies, QW8184 is well tolerated both in miceand rats with about a 3-fold increase in the maximum-tolerated-dose(MTD) over the current marketed drug formulation. Using the B16mouse melanoma model, a significant improvement in drug efficacywas observed with QW8184 over Taxol®. Conclusions. QW8184, a stable sub-micron o/w emulsion of paclitaxelhas been developed that can be filter-sterilized and administered i.v.as a bolus dose. When compared to Taxol®, this emulsion exhibitedreduced toxicity and improved efficacy most likely due to thecomposition and dependent physicochemical characteristics of the emulsion.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1007565230130
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 8
    Electronic Resource
    Electronic Resource
    Hydraulic analysis of free-surface flows with solidification (2000)
    Springer
    Archive of applied mechanics 70 (2000), S. 17-29 
    Details
    ISSN: 1432-0681
    Keywords: Key words free-surface flow ; solidification ; strip casting ; steady state ; nonuniqueness ; 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 paper is concerned with a one-dimensional analysis of plane open-channel flow with continuous solidification. The process is of relevance for recent developments in the casting of steel and other metals. The bottom of the channel consists of a rotating casting roll and a horizontal cooling table, where the solidified material is withdrawn with given velocity. The study is restricted to the region downstream of the top of the casting roll. Surface tension is neglected. In the main part of the analysis inviscid fluid flow is considered since the Reynolds number is very large in the applications. It is found that the steady-state solutions are nonunique in a certain parameter range. In addition to a continuous solution, there are two solutions including hydraulic jumps, with one hydraulic jump being located on the casting roll, the other one on the cooling table. Regarding the stability of the non unique solutions, the evolution of disturbances is investigated numerically as an initial-value problem. It is concluded that the hydraulic jump on the cooling table is unstable, while the other discontinuous solution as well as the continuous solution are stable for sufficiently small disturbances. Which stable solution is attained in the steady state, depends on the history of the process. Friction at the liquid/solid interface is taken into account in the last part of the analysis. A constant friction coefficient is assumed. It is found that the history of the process determines the steady-state solution if, and only if, the friction coefficient is sufficiently small. For larger values of the friction coefficient, the steady-state solution is unique and independent of the history of the transient process. Furthermore, for sufficiently large friction coefficients, stable hydraulic jumps are found, in contrast to the inviscid case, also on the cooling table.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004199900031
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 9
    Electronic Resource
    Electronic Resource
    Stability of Attractive Bose–Einstein Condensates (2000)
    Springer
    Journal of statistical physics 101 (2000), S. 731-746 
    Details
    ISSN: 1572-9613
    Keywords: attractive Bose–Einstein condensates ; nonlinear Schrödinger equation ; stability ; ground state ; variational arguments
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract We propose the critical nonlinear Schrödinger equation with a harmonic potential as a model of attractive Bose–Einstein condensates. By an elaborate mathematical analysis we show that a sharp stability threshold exists with respect to the number of condensate particles. The value of the threshold agrees with the existing experimental data. Moreover with this threshold we prove that a ground state of the condensate exists and is orbital stable. We also evaluate the minimum of the condensate energy.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1026437923987
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 10
    Electronic Resource
    Electronic Resource
    The Equation of State of Lakes (2000)
    Springer
    Aquatic geochemistry 6 (2000), S. 1-17 
    Details
    ISSN: 1573-1421
    Keywords: lakes ; density ; compressibility ; expansibility ; conductivity ; stability ; pvt properties
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract In recent years, a number of workers have studied the stability of deep lakes such as Lake Tanganyika, Lake Baikal and Lake Malawi. In this paper, the methods that can be used to determine the effect that the components of lakes have on the equation of state are examined. The PVT properties of Lakes have been determined by using apparent molal volume data for the major ionic components of the lake. The estimated PVT properties (densities, expansibility and compressibilities) of the lakes are found to be in good agreement with the PVT properties (P) of seawater diluted to the same salinity. This is similar to earlier work that showed that the PVT properties of rivers and estuarine waters could also be estimated from the properties of seawater. The measured densities of Lake Tanganyika were found to be in good agreement (± 2 × 10-6 g cm-3) with the values estimated from partial molal properties and the values of seawater at the same total salinity (ST = 0.568‰). The increase in the densities of Lake Tanganyika waters increased due to changes in the composition of the waters. The measured increase in the measured density (45 × 10-6 g cm-3) is in good agreement (46 × 10-6 g cm-3) with the values calculated for the increase in Na+, HCO3 -, Mg2+, Ca2+ and Si(OH)4. Methods are described that can be used to determine the conductivity salinity of lakes using the equations developed for seawater. By combining these relationships with apparent molal volume data, one can relate the PVT properties of the lake to those of seawater.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1009626325650
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 11
    Electronic Resource
    Electronic Resource
    Concerning a Technique for Increasing Stability of Climbing Robots (2000)
    Springer
    Journal of intelligent and robotic systems 27 (2000), S. 195-209 
    Details
    ISSN: 1573-0409
    Keywords: wall-climbing robot ; electromagnetic grippers ; stability ; additional support element ; sliding and turning over conditions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Legged-climbing robot is considered. Each foot of the robot has an electromagnet system for robot"s holding on a metal surface. This surface can be both vertical and inclined, including negative slope. Analytical calculation of robot stability under turn over or sliding conditions has been made. Critical slopes have been determined. One of these slopes corresponds to minimal reserve of robot stability towards sliding and another to minimal reserve of robot stability towards turning-over. As total reserve of stability of a robot is always equal to the minimal one of these reserves. Additional support elements of elastic material with high coefficient of friction, along with electromagnet, allows to increase minimal reserve of robot stability towards sliding. The use of such support elements leads to redistributing force of normal support reaction between electromagnet (which surface has low coefficient of friction) and additional support element (which surface has high coefficient of friction). It is just what leads to increasing the total friction force and as a consequence to increasing of minimal reserve of robot stability towards sliding.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1008158332368
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 12
    Electronic Resource
    Electronic Resource
    Shower Meteoroids: Constraints From Interplanetary Dust Particles And Leonid Meteors (2000)
    Springer
    Earth, moon and planets 88 (2000), S. 35-58 
    Details
    ISSN: 1573-0794
    Keywords: Chemistry ; interplanetary dust particles (IDPs) ; Leonids ; meteor trails ; meteoroids ; meteors ; structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The cometary Leonid meteoroids represent a size range in between largest carbon-richIDPs and the smallest CI meteorites. Their dustball structure and chemistry offer anopportunity to constrain hierarchical dust accretion inferred from petrologic studies ofaggregate and cluster IDPs. The Leonid shower meteoroids of known ``comet ejection''ages provide an opportunity to study space weathering of cometary dust over periodsof up to several hundred years. The meteors and aggregate and cluster IDPs displaycontinuous thermal modification of organics and volatile element (Na, K-bearing phases), that occur as discrete minerals and amorphous solids each different response during kinetically controlled ablation. Leonid meteoroids are not excessively Na-rich. The occurrences of Leonid meteors can now be accurate predicted and combined withknowledge better models for the settling rates, collections of surviving dust becomea comet nucleus-sampling mission.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1013862627781
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 13
    Electronic Resource
    Electronic Resource
    Activity and stability of Cu/ZnO/Al2O3 catalyst promoted with B2O3 for methanol synthesis (2000)
    Springer
    Catalysis letters 68 (2000), S. 55-58 
    Details
    ISSN: 1572-879X
    Keywords: promoting effect ; B2O3 ; Cu/ZnO/Al2O3 catalyst ; methanol synthesis ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The addition of B2O3 to a Cu/ZnO/Al2O3 catalyst increased the activity of the catalyst for methanol synthesis after an induction period during the reaction. The stability of the B2O3-containing Cu/ZnO/Al2O3 catalyst was greatly improved by the addition of a small amount of colloidal silica to the catalyst.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019010831562
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 14
    Electronic Resource
    Electronic Resource
    Stability and excitation of potassium promoter in iron catalysts – the role of KFeO2 and KAlO2 phases (2000)
    Springer
    Catalysis letters 67 (2000), S. 129-134 
    Details
    ISSN: 1572-879X
    Keywords: potassium desorption ; stability ; excitation ; iron catalyst ; Rydberg atoms
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Well‐characterized catalyst model compounds of KAlO2 and KFeO2 are investigated by thermal desorption of potassium from the material. The desorbing fluxes of ions, atoms and highly excited states (field ionizable Rydberg states) were studied with surface and field ionization detectors in a vacuum apparatus. From the Arrhenius plots the activation energies for desorption of K and K+ were determined. The chemical state of potassium at the surfaces is concluded to be: ionic on KAlO2 (with the K desorption barrier of 1.76 eV) and covalent on KFeO2 (barrier of 2.73 eV). These results agree with the data obtained earlier for industrial catalysts for ammonia and styrene production. They are interpreted in terms of the Schottky cycle, which is completed for KAlO2 and fails for KFeO2. This failure indicates a non‐equilibrium desorption process. K Rydberg states are only found to desorb from KFeO2, in agreement with the suggestion that such states in some way are responsible for the catalytic activity.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019013504729
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 15
    Electronic Resource
    Electronic Resource
    The Dynamics of a Fish Stock Exploited in Two Fishing Zones (2000)
    Springer
    Acta biotheoretica 48 (2000), S. 207-218 
    Details
    ISSN: 1572-8358
    Keywords: Dynamical population ; fishing efforts ; metapopulation ; time scales ; aggregation method ; equilibrium ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract This work presents a specific stock-effort dynamical model. The stocks correspond to two populations of fish moving and growing between two fishery zones. They are harvested by two different fleets. The effort represents the number of fishing boats of the two fleets that operate in the two fishing zones. The bioeconomical model is a set of four ODE's governing the fishing efforts and the stocks in the two fishing areas. Furthermore, the migration of the fish between the two patches is assumed to be faster than the growth of the harvested stock. The displacement of the fleets is also faster than the variation in the number of fishing boats resulting from the investment of the fishing income. So, there are two time scales: a fast one corresponding to the migration between the two patches, and a slow time scale corresponding to growth. We use aggregation methods that allow us to reduce the dimension of the model and to obtain an aggregated model for the total fishing effort and fish stock of the two fishing zones. The mathematical analysis of the model is shown. Under some conditions, we obtain a stable equilibrium, which is a desired situation, as it leads to a sustainable harvesting equilibrium, keeping the stock at exploitable densities.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010208910738
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 16
    Electronic Resource
    Electronic Resource
    A New ADI Scheme for Solving Three-Dimensional Parabolic Equations with First-Order Derivatives and Variable Coefficients (2000)
    Springer
    Journal of computational analysis and applications 2 (2000), S. 293-308 
    Details
    ISSN: 1572-9206
    Keywords: parabolic equations ; ADI scheme ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract An ADI scheme for solving three-dimensional parabolic equations withfirst-order derivatives and variable coefficients has been developed basedon our previous papers and the idea of the modified upwind differencescheme. This ADI scheme is second-order accurate and unconditionallystable. Further, a small parameter can be chosen which makes it suitablefor simulating fast-transient phenomena or for computations on fine spatialmeshes. The method is illustrated with numerical examples.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010108620966
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 17
    Electronic Resource
    Electronic Resource
    Bifurcation Phenomena from Standing Pulse Solutions in Some Reaction-Diffusion Systems (2000)
    Springer
    Journal of dynamics and differential equations 12 (2000), S. 117-167 
    Details
    ISSN: 1572-9222
    Keywords: singular perturbation ; standing pulses ; stability ; Hopf bifurcation ; reaction-diffusion system
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract Bifurcation phenomena from standing pulse solutions of the problem $$\varepsilon \tau u_t = \varepsilon ^2 u_{xx} + f(u,v),{\text{ }}v_t = v_{xx} + g(u,v)$$ is considered. ε(〉0) is a sufficiently small parameter and τ is a positive one. It is shown that there exist two types of destabilization of standing pulse solutions when τ decreases. One is the appearance of travelling pulse solutions via the static bifurcation and the other is that of in-phase breathers via the Hopf bifurcation. Furthermore which type of destabilization occurs first with decreasing τ is discussed for the piecewise linear nonlinearities f and g.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1009098719440
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 18
    Electronic Resource
    Electronic Resource
    Normal Form Invariants Around Spin-orbit Periodic Orbits (2000)
    Springer
    Celestial mechanics and dynamical astronomy 78 (2000), S. 227-241 
    Details
    ISSN: 1572-9478
    Keywords: stability ; normal form ; spin-orbit resonance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract We consider a model of spin-orbit interaction, describing the motion of an oblate satellite rotating about an internal spin-axis and orbiting about a central planet. The resulting second order differential equation depends upon the parameters provided by the equatorial oblateness of the satellite and its orbital eccentricity. Normal form transformations around the main spin-orbit resonances are carried out explicitly. As an outcome, one can compute some invariants; the fact that these quantities are not identically zero is a necessary condition to prove the existence of nearby periodic orbits (Birkhoff fixed point theorem). Moreover, the nonvanishing of the invariants provides also the stability of the spin-orbit resonances, since it guarantees the existence of invariant curves surrounding the periodic orbit.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1011161605935
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 19
    Electronic Resource
    Electronic Resource
    Determination of primary structure of amberjack myosin heavy chain and its relationship with structural stability of various fish myosin rods (2000)
    Springer
    Fish physiology and biochemistry 23 (2000), S. 283-294 
    Details
    ISSN: 1573-5168
    Keywords: amberjack ; myosin heavy chain ; cDNA ; α-helix ; coiled coils ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The structural stability of fish myosin depends upon species and temperatures of water in which fish live. Primary, secondary, and quaternary structures of myosin heavy chain (MyHC) from three species of fish living at different temperature ranges have been compared with those of rabbit MyHC in order to investigate the differences in stability. Primary structure of MyHC, although being accessible for warm-water and cold-water fish (carp and walleye pollack), was not available in previous for tropical-water fish literature; so in this study primary structure of MyHC of the tropical-water fish amberjack has been determined by cloning and sequencing its cDNA. The MyHC has 1938 amino acid residues (AA), which are almost as much as as those of carp and walleye pollack. The amberjack MyHC is 91–95% homologous with other fish and rabbit MyHCs. There is a discernible difference between animal species with stable myosin rod (amberjack, carp, and rabbit) and walleye pollack with unstable rod. Stable rod species have a high probability of forming coiled-coil around the COOH-terminal end of the rod, while the pollack has a low coiled-coil formation probability. In addition, the average scores of the coiled-coil for myosin rod were rabbit (1.738) 〉 amberjack (1.691) 〉 carp (1.680) 〉 walleye pollack (1.674) which correlated exactly with the observed stability. The results suggest that coiled-coil forming ability, particularly around the COOH-terminal end, directs structural stability of fish myosin rod.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1011176105285
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 20
    Electronic Resource
    Electronic Resource
    Destabilization for quasivariational inequalities of reaction-diffusion type (2000)
    Springer
    Applications of mathematics 45 (2000), S. 161-176 
    Details
    ISSN: 1572-9109
    Keywords: reaction-diffusion system ; unilateral conditions ; quasivariational inequality ; Leray-Schauder degree ; eigenvalue ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract We consider a reaction-diffusion system of the activator-inhibitor type with unilateral boundary conditions leading to a quasivariational inequality. We show that there exists a positive eigenvalue of the problem and we obtain an instability of the trivial solution also in some area of parameters where the trivial solution of the same system with Dirichlet and Neumann boundary conditions is stable. Theorems are proved using the method of a jump in the Leray-Schauder degree.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1023033910657
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 21
    Electronic Resource
    Electronic Resource
    Stabilization of smoothness priors time-varying autoregressive models (2000)
    Springer
    Circuits, systems and signal processing 19 (2000), S. 423-435 
    Details
    ISSN: 1531-5878
    Keywords: Time-varying autoregressive models ; stability ; smoothness priors ; Tihkonov regularization ; constrained optimization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The stability of time-varying autoregressive (AR) models is an important issue in such applications as time-varying spectrum estimation and electroencephalography simulation and estimation. In some cases, such as time-varying spectrum estimation, the models that exhibit roots near unit moduli are difficult to use. Thus a tighter stability condition such as stability with a positive margin is needed. A time-varying AR model is stable with a positive margin if the moduli of the roots of the time-varying characteristic polynomial are somewhat less than unity for every time instant. Recently, a new method for the estimation of the time-varying AR models was introduced. This method is based on the interpretation of the underdetermined time-varying prediction equations as an ill-posed inverse problem that is solved by Tikhonov regularization. The method is referred to as the deterministic regression smoothness priors (DRSP) scheme. In this paper, a stabilization method in which the DRSP scheme is augmented with nonlinear stability constrainst is proposed. The problem is formulated so that stability with a positive margin can also be achieved. The problem is solved iteratively with an exterior point algorithm. The performance of the algorithm is studied with a simulation. It is shown that the proposed approach is well suited to stable modeling of signals containing narrowband transitions.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01196156
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 22
    Electronic Resource
    Electronic Resource
    Evaluation of genotype, environment, and genotype-by-environment interaction for capsaicinoids in Capsicum annuum L. (2000)
    Springer
    Euphytica 111 (2000), S. 185-190 
    Details
    ISSN: 1573-5060
    Keywords: chile ; double haploid ; pepper ; pungency ; stability ; within-genotype variance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The response, in terms of capsaicinoid content, of chile (Capsicum annuum L.) genotypes to different environments was studied. Double haploidlines, an F1 hybrid, and an open-pollinated cultivar estimated the genotype, environment, and genotype-by-environment interaction effect on the total capsaicinoids and on individual capsaicinoids. Significant differences were observed among the genotypes and among genotype-by-environment interactions over the environments. Among the genotypes in an environment, the within-genotype variances were also significantly different. The double haploid line, HDA 207, had low within-genotype variance for individual and total capsaicinoids, with the exception of the isomer of dihydrocapsaicin. Also for HDA 270, the genotype-by-environment interaction was negligible for individual and total capsaicinoids, Indicating stability across environments.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1003837314929
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 23
    Electronic Resource
    Electronic Resource
    Recurrent selection in oat for adaptation to diverse environments (2000)
    Springer
    Euphytica 113 (2000), S. 195-205 
    Details
    ISSN: 1573-5060
    Keywords: Avena ; genetic correlation ; genotype-environmentinteraction ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract In order to test if selection can improve a population's adaptation to diverse environments simultaneously, three cycles of recurrent selection based on grain yield in Iowa, Idaho, and Norway were practiced in an oat (Avena sativaL.) population developed from North American, Scandinavian, and wild species (A. sterilis L.) germplasm sources. Specific objectives were to determine if selection: increased mean yields across environments and within all environments; changed the genetic correlation of yields in different environments; and changed genetic variation for yield within the population. We evaluated 100 to 210 randomly-chosen families from each cycle of selection at three Iowa locations, in Idaho, and in Norway for two years. Grain yield within each location and mean yields across locations increased significantly over cycles of selection. Mean yields across locations expressed as a percent of the original population mean increased at a rate of 2.6% per year. Several families from the third cycle population exhibited both high mean yields across locations and consistently high yields within all locations. Average genetic correlations of yield in different environments were higher in the second cycle than in the original population. A trend of reduced genetic variation and heritability was observed in Iowa only. These results suggest that we successfully improved mean population yield both within and across locations, and yield stability across environments, and in developing families with outstanding adaptation to diverse environments.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1003933421378
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 24
    Electronic Resource
    Electronic Resource
    Effects of Ca2+ on the Activity and Stability of Methanol Dehydrogenase (2000)
    Springer
    The protein journal 19 (2000), S. 469-473 
    Details
    ISSN: 1573-4943
    Keywords: Methanol dehydrogenase ; Ca2+ ; binding ; activity ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effects of exogenously added Ca2+ on the enzymatic activity and structural stability of methanol dehydrogenase were studied for various Ca2+ concentrations. Methanol dehydrogenase activity increased significantly with increasing concentration of Ca2+, approaching saturation at 200 mM Ca2+. The effect of Ca2+ on the activation of MDH was time dependent and Ca2+ specific and was due to binding of the metal ions to the enzyme. Addition of increasing concentration of Ca2+ caused a decrease of the intrinsic tryptophan fluorescence intensity in a concentration-dependent manner to a minimum at 200 mM, but with no change in the fluorescence emission maximum wavelength or the CD spectra. The results revealed that the activation of methanol dehydrogenase by Ca2+ occurred concurrently with the conformational change. In addition, exogenously bound Ca2+ destabilized MDH. The potential biological significance of these results is discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1026597314542
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 25
    Electronic Resource
    Electronic Resource
    Debonding of the interface as 'crack arrestor' (2000)
    Springer
    International journal of fracture 105 (2000), S. 57-79 
    Details
    ISSN: 1573-2673
    Keywords: Interface toughness ; interface debonding ; stability ; adhesive interface ; bimaterial.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In this paper, we studied the interface debonding when a crack perpendicularly approaches an interface between two dissimilar elastic materials. An interface toughness law was first defined according to an adhesive model governing the interface fracture. By analysing the interaction between the normally approaching crack and the interface crack and by tacking account of the adhesive forces at ends of the interfacial crack, a model for studying the interface debonding and the debonding stability was established. It is observed that the interface debonding toughness depends strongly on the mixed mode locally produced over the plastic adhesive zone of the interface. Moreover, the interface debonding may be unstable, i.e. the interface debonding length may jump from an initial value to a certain final value under critical remote loading. This jump may be surprisedly important in certain cases. These results agree with the experimental works gathered so far and can be used to explain the mechanism of 'crack arrestor' formed by an interface.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1007603809972
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 26
    Electronic Resource
    Electronic Resource
    Numerical Investigation of a Stability Theorem Arising from the 2-Dimensional Analysis of an Iterative Optimal Control Algorithm (2000)
    Springer
    Multidimensional systems and signal processing 11 (2000), S. 109-124 
    Details
    ISSN: 1573-0824
    Keywords: 2-D linear systems ; optimal control ; stability ; unit memory linear repetitive processes ; numerical methods
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Because many optimal control problems require solution using iterative procedures they fall naturally in the realm of 2-D systems where the two dimensions are response time horizon and iteration index, respectively. The paper uses this observation to employ 2-D systems theory, in the form of unit memory repetitive process techniques, to analyse local stability and convergence behaviour of a continuous optimal control algorithm based on dynamic system optimisation and parameter estimation. Existing work is extended to incorporate unmatched terminal constraints. Necessary and sufficient conditions for stability are obtained whose evaluation require the solution of a difficult eigenvalue problem. The paper shows how solutions can be achieved using numerical and graphical facilities of MATLAB.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1008490731182
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 27
    Electronic Resource
    Electronic Resource
    The Jump Behavior and Stability Analysis for 2-D Singular Systems (2000)
    Springer
    Multidimensional systems and signal processing 11 (2000), S. 339-358 
    Details
    ISSN: 1573-0824
    Keywords: 2-D systems ; descriptor systems ; singular systems ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: Abstract In this paper, we discussthe jump behavior and stability problems for 2-D linear shift-invariantsingular systems under the standard boundary conditions. It isshown that once a boundary condition or the input is inadmissiblein the classical sense, a group of non-causal or backward jumpsof the system states will be incited. This interpretation releasesthe conventional admissibility constraints on the boundary conditionsand inputs. Based on this observation, a systematic stabilitytheory is developed for 2-D singular systems. The well-knownbasic stability theorem for the 1-D singular systems or 2-D regularsystems is thus extended to the 2-D singular case.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1008429611994
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 28
    Electronic Resource
    Electronic Resource
    Structure, Mechanical Properties, and Mechanics of Intracranial Saccular Aneurysms (2000)
    Springer
    Journal of elasticity 61 (2000), S. 49-81 
    Details
    ISSN: 1573-2681
    Keywords: collagen structure ; stability ; rupture criterion ; growth mechanics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Intracranial saccular aneurysms remain an enigma; it is not known why they form, why they enlarge, or why only some of them rupture. Nonetheless, there is general agreement that mechanics plays an essential role in each aspect of the natural history of these potentially deadly lesions. In this paper, we review recent findings that discount limit point instabilities under quasi-static increases in pressure and resonance under dynamic loading as possible mechanisms of enlargement of saccular aneurysms. Indeed, recent histopathological data suggest that aneurysms enlarge due to a stress-mediated process of growth and remodeling of collagen, the primary load-bearing constituent within the wall. We submit that advanced theoretical, experimental, and numerical studies of this process are essential to further progress in treating this class of pathologies. The purpose of this review is to provide background and direction that encourages elasticians to contribute to this important area of research.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010989418250
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 29
    Electronic Resource
    Electronic Resource
    Perron–Frobenius Theory and Symmetry of Solutions to Nonlinear PDE's (2000)
    Springer
    Letters in mathematical physics 53 (2000), S. 313-320 
    Details
    ISSN: 1573-0530
    Keywords: partial differential equations ; nonlinearities ; symmetries ; stability ; minimization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics , Physics
    Notes: Abstract We suggest a simple but general method of establishing symmetry properties of stable solutions of nonlinear elliptic equations. The method relies on characterization of symmetry breaking with a help of zero modes and on a generalization of the Perron–Frobenius theory.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1007622208894
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 30
    Electronic Resource
    Electronic Resource
    On the Robust Stability of 2D Schur Polynomials (2000)
    Springer
    Journal of optimization theory and applications 106 (2000), S. 431-439 
    Details
    ISSN: 1573-2878
    Keywords: multidimensional polynomial theory ; robustness ; Kharitonov theorem ; stability ; Schur polynomials ; inverse Kharitonov problem ; Rouché theorem
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract In this note, the problem of the robust stability for a two-dimensional (two-variable) Schur polynomial which is the characteristic polynomial of a discrete-time linear time-invariant system is investigated. A new approach based on the Rouché theorem is adopted. The extension to the robust stability for multidimensional (multivariable) polynomials is also provided. Interesting sufficient conditions for such robust stability are derived. A two-dimensional example is included to support the theoretical result.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1004615917160
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 31
    Electronic Resource
    Electronic Resource
    Upper and Lower Semicontinuity for Set-Valued Mappings Involving Constraints (2000)
    Springer
    Journal of optimization theory and applications 106 (2000), S. 527-550 
    Details
    ISSN: 1573-2878
    Keywords: vector optimization ; set-valued mappings ; constraint sets ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract In vector optimization, several authors have studied the upper and lower semicontinuity for mappings involving constraints in topological vector spaces partially ordered through a cone with nonempty interior. In this paper, we give conditions about the upper and lower semicontinuity in the case that the ordering cone in the parameter space has possibly empty interior, as it happens in many function spaces and seqence spaces.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1004653312019
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 32
    Electronic Resource
    Electronic Resource
    Mixed Solutions for Weak Stackelberg Problems: Existence and Stability Results (2000)
    Springer
    Journal of optimization theory and applications 105 (2000), S. 417-440 
    Details
    ISSN: 1573-2878
    Keywords: mixed solutions ; weak Stackelberg problems ; existence ; stability ; weak convergence of probability measures
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract We are concerned with ∈-mixed solutions for weak Stackelberg problems corresponding to two-player nonzero-sum noncooperative games. Two cases are considered: (i) mixed strategies for only the second player; (ii) mixed strategies for both players. After giving basic results relating convergence of functions and weak convergence of probability measures, we establish existence and stability results for ∈-mixed solutions under general assumptions of minimal character without any convexity assumption. Our results improve previous work of Mallozzi and Morgan (Refs. 1–2).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1004618103646
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 33
    Electronic Resource
    Electronic Resource
    Optimum Radius of Robust Stability for Schur Polynomials (2000)
    Springer
    Journal of optimization theory and applications 104 (2000), S. 165-174 
    Details
    ISSN: 1573-2878
    Keywords: Systems theory ; stability ; robust stability ; linear systems ; discrete-time systems ; robustness ; polynomial theory ; Kharitonov theorem ; inverse Kharitonov problem ; Rouche theorem
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract The paper investigates the problem of the robust stability of Schur polynomials. Recently, a new approach based on the Rouche theorem of classical complex analysis has been adopted for the solution of this problem. In this paper, an improvement of the previous solution is presented. This is the optimum solution of the robust stability problem for Schur polynomials, which is obtained by solving a minimization problem and is better than other methods in robust stability literature. Three numerical examples are given to illustrate the proposed method.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1004684907724
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 34
    Electronic Resource
    Electronic Resource
    Extended Well-Posedness Properties of Vector Optimization Problems (2000)
    Springer
    Journal of optimization theory and applications 106 (2000), S. 165-182 
    Details
    ISSN: 1573-2878
    Keywords: Vector optimization ; asymptotically minimizing sequences ; extended well-posedness ; stability ; vector variational principle
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract In this paper, the concept of extended well-posedness of scalar optimization problems introduced by Zolezzi is generalized to vector optimization problems in three ways: weakly extended well-posedness, extended well-posedness, and strongly extended well-posedness. Criteria and characterizations of the three types of extended well-posedness are established, generalizing most of the results obtained by Zolezzi for scalar optimization problems. Finally, a stronger vector variational principle and Palais-Smale type conditions are used to derive sufficient conditions for the three types of extended well-posedness.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1004615325743
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 35
    Electronic Resource
    Electronic Resource
    Stability Properties of a Bond Portfolio Management Problem (2000)
    Springer
    Annals of operations research 99 (2000), S. 251-265 
    Details
    ISSN: 1572-9338
    Keywords: stochastic programming ; bond portfolio management ; interest ratescenarios ; stability ; sensitivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics , Economics
    Notes: Abstract The bond portfolio management problem is formulated as a multiperiod two-stage or multistage stochastic program based on interest rate scenarios. These scenarios depend on the available market data, on the applied estimation and sampling techniques, etc., and are used to evaluate coefficients of the resulting large scale mathematical program. The aim of the contribution is to analyze stability and sensitivity of this program on small changes of the coefficients – the (scenario dependent) values of future interest rates and prices. We shall prove that under sensible assumptions, the scenario subproblems are stable linear programs and that also the optimal first-stage decisions and the optimal value of the considered stochastic program possess acceptable continuity properties.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019275817688
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 36
    Electronic Resource
    Electronic Resource
    A Multiclass Feedback Queueing Network with a Regular Skorokhod Problem (2000)
    Springer
    Queueing systems 36 (2000), S. 327-349 
    Details
    ISSN: 1572-9443
    Keywords: multiclass networks ; networks with feedback ; Skorokhod Problem ; Skorokhod Mapping ; Lipschitz continuity ; stability ; load conditions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science
    Notes: Abstract We consider a four-class two-station network with feedback, with fluid inputs and a head-of-the-line generalized processor sharing discipline at each station. We derive the Skorokhod Problem associated with the network and obtain algebraic sufficient conditions for Lipschitz continuity of the associated Skorokhod Map. This provides the first example of a multiclass network with feedback for which the associated Skorokhod Problem has been proved to be regular. As an elementary application, we show that under the conditions which guarantee Lipschitz continuity the network is stable if and only if the usual load conditions apply.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1011037419624
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 37
    Electronic Resource
    Electronic Resource
    Performance analysis of a slotted-ALOHA protocol on a capture channel with fading (2000)
    Springer
    Queueing systems 34 (2000), S. 1-35 
    Details
    ISSN: 1572-9443
    Keywords: multiple access ; CDMA ; rates of convergence ; stability ; functional limit theorems ; transient analysis ; Markov-modulated capture channel
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science
    Notes: Abstract We consider the slotted ALOHA protocol on a channel with a capture effect. There are M 〈 ∞ users each with an infinite buffer. If in a slot, i packets are transmitted, then the probability of a successful reception of a packet is q i. This model contains the CDMA protocols as special cases. We obtain sufficient rate conditions, which are close to necessary for stability of the system, when the arrival streams are stationary ergodic. Under the same rate conditions, for general regenerative arrival streams, we obtain the rates of convergence to stationarity, finiteness of stationary moments and various functional limit theorems. Our arrival streams contain all the traffic models suggested in the recent literature, including the ones which display long range dependence. We also obtain bounds on the stationary moments of waiting times which can be tight under realistic conditions. Finally, we obtain several results on the transient performance of the system, e.g., first time to overflow and the limits of the overflow process. We also extend the above results to the case of a capture channel exhibiting Markov modulated fading. Most of our results and proofs will be shown to hold also for the slotted ALOHA protocol without capture.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1019192600091
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 38
    Electronic Resource
    Electronic Resource
    On the Robustness of Gaussian Elimination with Partial Pivoting (2000)
    Springer
    BIT 40 (2000), S. 62-73 
    Details
    ISSN: 1572-9125
    Keywords: Gaussian elimination ; stability ; pivoting
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract It has been recently shown that large growth factors might occur in Gaussian Elimination with Partial Pivoting (GEPP) also when solving some plausibly natural systems. In this note we argue that this potential problem could be easily solved, with much smaller risk of failure, by very small (and low cost) modifications of the basic algorithm, thus confirming its inherent robustness. To this end, we first propose an informal model with the goal of providing further support to the comprehension of the stability properties of GEPP. We then report the results of numerical experiments that confirm the viewpoint embedded in the model. Basing on the previous observations, we finally propose a simple scheme that could be turned into (even more) accurate software for the solution of linear systems.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1022314201484
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 39
    Electronic Resource
    Electronic Resource
    Stochastic Methods for Ill-Posed Problems (2000)
    Springer
    BIT 40 (2000), S. 226-240 
    Details
    ISSN: 1572-9125
    Keywords: Stochastic differential equations ; regularisation ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract This paper is devoted to the numerical analysis of ill-posed problems of evolution equations in Banach spaces using certain classes of stochastic one-step methods. The linear stability properties of these methods are studied. Regularisation is given by the choice of the regularisation parameter as α = $$\sqrt {\tau _n }$$ , where τ n is the stepsize and provides the convergence on smooth initial data. The case of the approximation of well-posed problems is also considered.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1022386822865
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 40
    Electronic Resource
    Electronic Resource
    Runge-Kutta Methods for the Numerical Solution of Stiff Semilinear Systems (2000)
    Springer
    BIT 40 (2000), S. 611-639 
    Details
    ISSN: 1572-9125
    Keywords: Runge-Kutta methods ; stability ; convergence ; stiff problems
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract This paper studies the stability and convergence properties of general Runge-Kutta methods when they are applied to stiff semilinear systems y′(t) = J(t)y(t) + g(t, y(t)) with the stiffness contained in the variable coefficient linear part. We consider two assumptions on the relative variation of the matrix J(t) and show that for each of them there is a family of implicit Runge-Kutta methods that is suitable for the numerical integration of the corresponding stiff semilinear systems, i.e. the methods of the family are stable, convergent and the stage equations possess a unique solution. The conditions on the coefficients of a method to belong to these families turn out to be essentially weaker than the usual algebraic stability condition which appears in connection with the B-stability and convergence for stiff nonlinear systems. Thus there are important RK methods which are not algebraically stable but, according to our theory, they are suitable for the numerical integration of semilinear problems. This paper also extends previous results of Burrage, Hundsdorfer and Verwer on the optimal convergence of implicit Runge-Kutta methods for stiff semilinear systems with a constant coefficients linear part.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1022332200092
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 41
    Electronic Resource
    Electronic Resource
    Stability of Linear Inequality Systems Measured by the Hausdorff Metric (2000)
    Springer
    Set-valued analysis 8 (2000), S. 253-266 
    Details
    ISSN: 1572-932X
    Keywords: Hausdorff metric ; linear inequality systems ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract In this paper, we propose a Hausdorff metric to measure the “distance” between two linear inequality systems on a real normed space X. For this topology, which comes through a pseudo-metric in the set Σ of linear inequality systems, the closedness of the feasible set mapping is studied, and at the same time a characterization of the stability of the subset Σ c of consistent sytems is given.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1008701026782
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 42
    Electronic Resource
    Electronic Resource
    Diagonally implicit Runge–Kutta methods for 3D shallow water applications (2000)
    Springer
    Advances in computational mathematics 12 (2000), S. 229-250 
    Details
    ISSN: 1572-9044
    Keywords: numerical analysis ; shallow water problems ; DIRK methods ; stability ; 65L06 ; 65L20 ; 65M12 ; 65M20
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract We construct A‐stable and L‐stable diagonally implicit Runge–Kutta methods of which the diagonal vector in the Butcher matrix has a minimal maximum norm. If the implicit Runge–Kutta relations are iteratively solved by means of the approximately factorized Newton process, then such iterated Runge–Kutta methods are suitable methods for integrating shallow water problems in the sense that the stability boundary is relatively large and that the usually quite fine vertical resolution of the discretized spatial domain is not involved in the stability condition.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1018969203026
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 43
    Electronic Resource
    Electronic Resource
    On the Stability of Functional Equations and a Problem of Ulam (2000)
    Springer
    Acta applicandae mathematicae 62 (2000), S. 23-130 
    Details
    ISSN: 1572-9036
    Keywords: stability ; functional equations ; Cauchy difference ; semigroup ; inequalities ; approximate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract In this paper, we study the stability of functional equations that has its origins with S. M. Ulam, who posed the fundamental problem 60 years ago and with D. H. Hyers, who gave the first significant partial solution in 1941. In particular, during the last two decades, the notion of stability of functional equations has evolved into an area of continuing research from both pure and applied viewpoints. Both classical results and current research are presented in a unified and self-contained fashion. In addition, related problems are investigated. Some of the applications deal with nonlinear equations in Banach spaces and complementarity theory.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1006499223572
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 44
    Electronic Resource
    Electronic Resource
    Stability of constant coefficient linear singular systems with delay (2000)
    Springer
    Circuits, systems and signal processing 19 (2000), S. 13-25 
    Details
    ISSN: 1531-5878
    Keywords: Singular systems ; delay ; consistency condition ; stability ; instability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: Abstract In this paper, the general class of singular systems with delay and linear constant coefficient singular systems with delay are discussed. First, several definitions of stability are presented for singular systems with delay, and general sufficient stability conditions and instability conditions are obtained. Second, stability and instability are analyzed for linear constant coefficient singular systems with delay.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01229989
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 45
    Electronic Resource
    Electronic Resource
    Stability and Hopf Bifurcation of Four-Wheel-Steering Vehicles Involving Driver's Delay (2000)
    Springer
    Nonlinear dynamics 22 (2000), S. 361-374 
    Details
    ISSN: 1573-269X
    Keywords: 4WS vehicle ; time delay ; stability ; Hopf bifurcation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract A mathematical model is presented for four-wheel-steeringvehicles, with the time delay in driver's response and the nonlinearityin lateral tyre forces taken into account. It is proved that thevehicle-driver system has a trivial steady state motion, as well aseight non-trivial steady state motions due to the nonlinearity of tyreforces. The asymptotic stability and Hopf bifurcation of the trivialsteady state are analyzed for two control strategies ofrear-wheel-steering. It is shown through the numerical simulations thatthe four-wheel-steering technique based on the bilinear control strategyworks better when the driver's response involves time delay.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1008324311249
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 46
    Electronic Resource
    Electronic Resource
    Study of Stability of a Stochastic Model of the "Dangling Spider" Problem. III (2000)
    Springer
    Cybernetics and systems analysis 36 (2000), S. 916-924 
    Details
    ISSN: 1573-8337
    Keywords: stochastic model ; "dangling spider problem" ; stability ; Lyapunov-Krasovskii functional
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science
    Notes: Abstract To study the stability of the stochastic "dangling spider" model, the second Lyapunov method is substantiated for stochastic differential functional equations with the entire previous history.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1009469729630
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 47
    Electronic Resource
    Electronic Resource
    1,3-Dihydrobenzo[c]thienylium (thiophthalylium) salts. (Review) (2000)
    Springer
    Chemistry of heterocyclic compounds 36 (2000), S. 115-133 
    Details
    ISSN: 1573-8353
    Keywords: thiophthalylium salts ; methods of preparation ; structure ; stability ; reactivity ; electrophilic properties
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Methods of preparation, chemical reactions, the structures and reactivity of thiophthalylium ions are reviewed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02283539
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 48
    Electronic Resource
    Electronic Resource
    Solving A $$\underline x $$ = $$\underline b $$ Using a Modified Conjugate Gradient Method Based on Roots of A (2000)
    Springer
    Journal of scientific computing 15 (2000), S. 441-456 
    Details
    ISSN: 1573-7691
    Keywords: modified conjugate gradient method ; conjugate gradient method ; Krylov space ; convergence rate ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science
    Notes: Abstract We consider the modified conjugate gradient procedure for solving A $$\underline x $$ = $$\underline b $$ in which the approximation space is based upon the Krylov space associated with A 1/p and $$\underline b $$ , for any integer p. For the square-root MCG (p=2) we establish a sharpened bound for the error at each iteration via Chebyshev polynomials in $$\sqrt A$$ . We discuss the implications of the quickly accumulating effect of an error in $$\sqrt A$$ $$\underline b $$ in the initial stage, and find an error bound even in the presence of such accumulating errors. Although this accumulation of errors may limit the usefulness of this method when $$\sqrt A$$ $$\underline b $$ is unknown, it may still be successfully applied to a variety of small, “almost-SPD” problems, and can be used to jump-start the conjugate gradient method. Finally, we verify these theoretical results with numerical tests.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1011132730828
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 49
    Electronic Resource
    Electronic Resource
    Associative Memories in Infinite Dimensional Spaces (2000)
    Springer
    Neural processing letters 12 (2000), S. 129-144 
    Details
    ISSN: 1573-773X
    Keywords: associative memory ; dynamical systems ; Glauber dynamics ; Hopfield model ; infinite dimensional state space ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science
    Notes: Abstract A generalization of the Little–Hopfield neural network model for associative memories is presented that considers the case of a continuum of processing units. The state space corresponds to an infinite dimensional euclidean space. A dynamics is proposed that minimizes an energy functional that is a natural extension of the discrete case. The case in which the synaptic weight operator is defined through the autocorrelation rule (Hebb rule) with orthogonal memories is analyzed. We also consider the case of memories that are not orthogonal. Finally, we discuss the generalization of the non deterministic, finite temperature dynamics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1009689025427
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
    Fulltext
  • 50
    Electronic Resource
    Electronic Resource
    Microporous Titanosilicates and other Novel Mixed Octahedral-Tetrahedral Framework Oxides (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 801-818 
    Details
    ISSN: 1434-1948
    Keywords: Zeolites ; Microporous zeolites ; Titanosilicates ; Transition metal ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stable microporous materials, such as zeolites, are extremely important for applications in catalysis, adsorption, ion-exchange, and separation. In this review we describe a new class of stable microporous materials that involves novel mixed octhaedral-tetrahedral framework oxides. The archetypal material is based on titanosilicates, although there is tremendous scope for introducing many other transition metals. These materials not only have potential novel applications in the fields normally associated with zeolites but also possible applications in the areas of optoelectronics, nonlinear optics, batteries, magnetic materials and sensors.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 51
    Electronic Resource
    Electronic Resource
    Ammonolysis of Trichlorosilanes (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 827-830 
    Details
    ISSN: 1434-1948
    Keywords: Ammonolysis ; Chlorine ; Nitrogen ; Silicon ; Silsesquiazane ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ammonolysis of trichlorosilanes RSiCl3 [R = CH(SiMe3)2 (1a), Ph (1b), Et (1c)] leads to a series of condensed products such as six-membered rings [(Me3Si)2CHSi(OH)NH]3 (2a) and [PhSi(NH2)NH]3 (2b), disilazane [(Me3Si)2CHSi(NH2)2]2NH (3) and the cage compound (EtSi)6(NH)9 (4). The mixed Si-N-O compound 2a was obtained when liquid ammonia was not dried over sodium prior to use. The reaction with sodium gives NaCl instead of NH4Cl as a by-product which is easily removed by filtration.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 52
    Electronic Resource
    Electronic Resource
    A New Approach to Well-Ordered Quantum Dots (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 835-837 
    Details
    ISSN: 1434-1948
    Keywords: Gold ; Clusters ; Quantum dots ; Monolayers ; Amphiphiles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Extended ordered monolayers of ligand stabilized Au55 clusters are formed at the phase boundary between water and dichloromethane. The water phase, containing amphiphilic molecules like per-6-deoxy-6-thio-α-cyclodextrin (1) or poly(vinylpyrrolidone) (2), is covered by a thin film of a solution of [Au55(PPh3)12Cl6] in dichloromethane. The interaction of the cluster molecules with the thiol functions of 1 or the polymer chains of 2 form perfect cluster orders of hexagonal and cubic structure. The monolayers can be transferred onto solid substrates by a simple dipping process. The use of carbon coated copper grids allows the investigation of the monolayers by transmission electron microscopy (TEM). Electron diffraction experiments under a microscope prove the hexagonal and cubic arrangements. The reason for the formation of the one or the other modification is still unknown.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 53
    Electronic Resource
    Electronic Resource
    Unprecedented Coordination of 4,4′,5,5′-Tetramethyl-2,2′-biphosphinine Doubly Bridging over an Open Triosmium Core (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 843-845 
    Details
    ISSN: 1434-1948
    Keywords: Triosmium cluster ; Biphosphinine ; Crystal structure ; Cyclic voltammetry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structure of the novel cluster [Os3(CO)10(4,4′,5,5′-tetramethyl-2,2′-biphosphinine)] reveals an unprecedented coordination mode of the biphosphinine ligand that occupies a doubly-bridging position spanning the open osmium triangle. The cluster is photostable, pointing to a localization of the lowest-energy electronic transition largely on the negatively charged biphosphinine ligand.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 54
    Electronic Resource
    Electronic Resource
    Temperature-Dependent Photophysical, Photochemical and Redox Properties of Novel Complexes (CO)2CpRu-Ru(Ln)-RuCp(CO)2 and (CO)2CpRu-Ru(Ln)-SnPh3 [Ln = (CO)2(N,N′-diisopropyl-1,4-diaza-1,3-butadiene)] (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 847-855 
    Details
    ISSN: 1434-1948
    Keywords: Photochemistry ; Electrochemistry ; Ruthenium compounds ; α-Diimine complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photophysical, photochemical and redox properties of the title complexes were investigated. Resonance Raman measurements revealed the lowest-energy electronic transition to possess σ→π* character. At low temperatures, long-lived near-IR emission was observed. Irradiation in solution results in homolytic splitting of a Ru-Ru bond as the primary step, followed by secondary reactions of the radical fragments depending on the experimental conditions. (Spectro)electrochemical investigations of the title species proved that the axial [RuCp(CO)2] groups exert a stabilising influence on the corresponding radical cations, while destabilising the corresponding radical anions, compared to the redox behaviour of other ruthenium complexes of this type.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 55
    Electronic Resource
    Electronic Resource
    In situ NMR Detection of Dihydrides in the Systems [RhH(SnCl3)5]3-/Tertiary Phosphanes/Parahydrogen (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 889-894 
    Details
    ISSN: 1434-1948
    Keywords: Rhodium hydride complexes ; Parahydrogen ; Tin ligands ; Hydrogenations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidative addition of dihydrogen to the [RhH(SnCl3)5]3-/PR3 system (PR3 = PPh3, PEtPh2, PEt3) leads to the formation of previously unknown dihydride complexes, the 1H-NMR spectra of which have been studied by means of the ParaHydrogen Induced Polarization (PHIP) method. The composition of the resulting complexes crucially depends on the type of the added phosphane. With PEt3 as the phosphane and acetonitrile as the solvent, a complex with a SnCl2L ligand (L = CD3CN) can be detected. All systems examined catalyze the hydrogenation of phenylacetylene. During these reactions, both the 1H-NMR resonances of the dihydride complexes and those of styrene, the hydrogenation product of phenylacetylene, can be detected simultaneously. In the case of SnBr3 ligands, hydrogen addition in the presence of phosphanes leads to similar dihydride complexes, which were also identified via 1H-NMR spectroscopy. Furthermore, a mixed complex of the structure [Rh(SnBr3)nBr6-n]3- has been isolated.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 56
    Electronic Resource
    Electronic Resource
    How to Find Correlations Between Molecular Shape and Packing in a Molecular Crystal: Application of a Novel Strategy to Recognize n-Point Polyhedra in Three-Dimensional Space (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 857-877 
    Details
    ISSN: 1434-1948
    Keywords: Crystal packing ; Neural networks ; Pattern recognition ; Organometallic compounds ; Close packing ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structures of hundreds of thousands of molecular compounds have now been determined with the quantitative information being stored in large databases. Chemists are generally interested in that specific part of this information which refers to individual molecules. The packing of molecules and their spatial relation to each other is not the focus of interest, even though the material properties of a molecular crystal are determined by both the packing arrangement of the molecules and their specific properties. The lack of interest in packing has at least one obvious reason. It is difficult for the non-expert to find the appropriate packing categories when looking at a principally infinite lattice. A tool performing this search for individual categories of packing in an automatic manner would therefore be of general importance. The development and application of such a tool is described in this paper. Novel strategies to extract a set of n points forming a specific n-point polyhedron from a set of p points (p 〉 n) is at its basis. Neural networks and second moment analysis are used as the methods of pattern recognition. In order to correlate packing and shape, second moment analysis of molecular shape is also used. This novel method is applied to three classes of organometallic compounds to determine whether the crystals formed by these compounds belong to any of the three classes fcc, bcc, or hcp in an idealized sense. A strong correlation is found between molecular shape and the membership or nonmembership of these classes. The corresponding program, including appropriate tools for visual representation, is available from the authors.
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 57
    Electronic Resource
    Electronic Resource
    Tricarbonyl-η6-[(2-thiophenyl)arene]- and -η6-[(2-thiophenyl)carbonylarene]- chromium Complexes: Preparation and Conformational Study (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 901-905 
    Details
    ISSN: 1434-1948
    Keywords: Arenetricarbonyl chromium complexes ; Palladium ; Cross coupling reaction ; Thiophenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cross coupling reaction of (p-chloroanisole)tricarbonylchromium complex (1) with thiophene derivatives under palladium-catalyzed conditions leads to the selective formation of tricarbonyl-η6-[(2-thiophenyl)arene]- or -η6-[(2-thiophenyl)carbonylarene]chromium complexes (2 or 3) depending on reaction conditions. The conformation of complexes 2 and 3 in the solid state as well as in solution are reported.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 58
    Electronic Resource
    Electronic Resource
    Electrochemical and Spectroscopic Properties of Cyclometallated and Non-Cyclometallated Ruthenium(II) Complexes Containing Sterically Hindering Ligands of the Phenanthroline and Terpyridine Families (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 113-119 
    Details
    ISSN: 1434-1948
    Keywords: Ruthenium ; Phenanthroline ; Luminescence ; Sterically hindered ligands ; Terpyridine ; Cyclometallation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two series of cyclometallated and noncyclometallated ruthenium(II) complexes incorporating mono- or disubstituted 1,10-phenanthroline- and 2,2′:6′,2′′-terpyridine-type ligands have been synthesized and characterized. An X-ray crystal structure for one of the complexes, Ru(ttpy)(mapH)-(Cl)(PF6), has been obtained (mapH = 2-p-anisyl-1,10-phenanthroline; ttpy = 4′-tolyl-2,2′:6′,2′′-terpyridine). Distinct electrochemical and photophysical properties have been observed for the two series: a remarkable feature is the observation of relatively long-lived MLCT excited states (from 70 to 106 ns at room temperature in CH3CN) for three of the cyclometallated complexes. A discussion is given on the role of factors like sigma donation by the cyclometallating ligands, interligand steric hindrance and interligand π-π interactions that affect the electrochemical and spectroscopic properties.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 59
    Electronic Resource
    Electronic Resource
    Two Examples of Novel and Unusual Double-Layered, Two-Dimensional CuII Compounds with Bridging 1,3-Bis(1,2,4-triazol-1-yl)propane (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 121-126 
    Details
    ISSN: 1434-1948
    Keywords: Polymeric copper complexes ; Group-subgroup relationships ; 2D-sheets ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and characterisation of two new polymeric CuII complexes is described, i.e. {[Cu(btp)2(CH3CN)(H2O)](CF3SO3)2}n (1) and {[Cu(btp)2(CH3CN)2](ClO4)2}n (2), in which btp = [1,3-bis(1,2,4-triazol-1-yl)propane]. Compound 1 crystallizes in space group P21/c with a = 11.9337(15) Å, b = 20.108(6) Å, c = 12.748(6) Å, β = 92.247(14)°, and Z = 4. Compound 2 crystallizes in space group Pna21 with a = 18.770(8) Å, b = 12.648(8) Å, and c = 12.019(8) Å. The structures refined to R1 values of 0.0683 for 1 and 0.0846 for 2. In both structures the CuII ions are linked by the bridging ligands, resulting in two-dimensional networks. Two such curved layers are arranged on top of each other with center-to-center of layer distances of 2.12 Å in 1 and 1.98 Å in 2. Such double layers are separated from each other by 10.05 Å in 1 and 9.385 Å in 2. The space between the double layers is occupied with interstitial anions. No significant interaction between CuII ions is observed by EPR and magnetic susceptibility measurements. The compounds form a new class of a lattice engineered system held together by the CuII ions. - The coordination geometry of the copper ions is distorted octahedral, with the equatorial plane formed by the N4 nitrogens of the four triazole groups and the axial sites occupied by solvent molecules; acetonitrile and water in structure 1 and two acetonitrile molecules in structure 2. The two structures are related by a group-subgroup relationship, which appears to be the first such case in supramolecular chemistry. - The Cu-N vibrations in the FIR region are found at 274 cm-1 for 1, and at 276 cm-1 for 2. The ligand-field maxima are observed at about 16·103 cm-1, with a shoulder at about 12·103 cm-1. The νCN stretching vibrations of the acetonitrile molecules are found at 2303 and 2261 cm-1 for 1, and at 2313, 2294, 2278, and 2260 cm-1 for 2.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99211_s.pdf or from the author.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 60
    Electronic Resource
    Electronic Resource
    Mechanisms of Cyclopalladation Reactions in Acetic Acid: Not So Simple One-Pot Processes (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 217-224 
    Details
    ISSN: 1434-1948
    Keywords: Reaction mechanisms ; Cyclopalladation ; Acetic acid ; Pd-C bond stability ; Polynuclear species ; Palladium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The processes operating during the synthetic cyclopalladation reactions of imines in acetic acid have been studied from a kinetico-mechanistic point of view. These reactions include a fast initial coordination to the palladium through the N-donor atom of the imine, followed by the proper C-H bond activation to produce the acetato bridged dimeric species. At this point, the lability of the bridging acetato groups, the hydrolysis of the C-Pd bonds, and/or the hydrolysis of C=N exo bonds contribute to the generation of dark red polynuclear compounds. The processes occurring after the C-H activation have been followed kinetically, both from palladium acetate plus imine, and the synthetically pure isolated acetato dimers as starting materials. The kinetic and activation parameters have been found identical within experimental error whatever the starting material was (k323 = 1.5 × 10-4 s-1; ΔH# = 51 kJ mol-1; ΔS# = -163 JK-1 mol-1 ΔV# = +19 cm3 mol-1 for the 4-ClC6H4-CH=N-CH2-C6H5 imine derivative 1a). Acidolysis of C-Pd bonds has been found to occur in these polynuclear species. When alternative monomeric Cbenzylic-Pd bond-containing complexes are possible follow ups of the reactions produce them as final dead-end complexes (k323 = 2.2 × 10-5 s-1; ΔH# = 61 kJ mol-1; ΔS# = JK-1 mol-1 ΔV# ≈ 0 cm3 cm-1 for the [2,4,6-(CH3)3]C6H2-CH=N-CH2-[2-(CH3]C6[H4] imine derivative 3d). The same study has been carried out with primary amines in order to check the validity of the data if C=N bond hydrolysis is taking place in the imine derivatives with exo C=N bonds. For complexes with similar type of metallacycles, the results agree reasonably well with the proposed mechanism [k323 = 1.2·10-4 s-1, ΔH# = 46 kJ·mol-1, ΔS# = -180 J·K-1mol-1, ΔV# = -16 cm3·mol-1 for the polynuclear formation of the C6H5-CH2-NH2 derivative 4e; k323 = 3.0·10-4 s-1, ΔH# = 55 kJ·mol-1, ΔS
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 61
    Electronic Resource
    Electronic Resource
    Nickel Chelate Complexes of 2-Alkylphenylphosphanylphenolates: Synthesis, Structural Investigation and Use in Ethylene Polymerization (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 299-305 
    Details
    ISSN: 1434-1948
    Keywords: Phosphanylphenolate ; Cyclopentadienylnickel complexes ; Chelates ; Ethylene polymerization ; Crystal structure ; Polymerizations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Diphenylphosphanyl- and 2-alkylphenylphosphanyl-4-methylphenols 1 or their silyl ethers 2 and equimolar amounts of nickelocene react in benzene preferably to give orange-brown diamagnetic cyclopentadienylnickel chelate complexes [η-CpNi(P∩O)] (3). Addition of a second equivalent of 1 or 2 affords (RR) and (SS) diastereoisomers of cis-bis(P∩O-chelates) 4a-c (R = Ph, Me, iPr) or the unsymmetrical cis-bis(P∩O-chelate) 5, whereas with bulkier substituted derivatives 1d or 2d (R = tBu) the second step is hindered or retarded. The reactivity of 1d remains high towards nickel salts in polar solvents, but in contrast to 1a-c, yielding 4, a sparingly soluble green trans-bis(P-O-chelate) nickel complex 6d is formed. Complexes formed in situ from 1 or 2 and Ni(COD)2 in toluene catalyze the polymerization of ethylene. The cyclopentadienyl (P∩O) complexes 3, however, are too stable to be active in this process. The crystal and molecular structure of 3c and 4c are described.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99035_s.pdf or from the author.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 62
    Electronic Resource
    Electronic Resource
    Chiral Ruthenium-Sulfene Complexes - Synthesis and C-C Coupling Reactions (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 287-297 
    Details
    ISSN: 1434-1948
    Keywords: Enolates ; Nucleophilic additions ; Ruthenium ; S ligands ; Sulfenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of the chiral racemic complex [CpRu(mppe)(SO2)]PF6 (1, mppe = Me2PC2H4PPh2) with diazomethane or -ethane gave the sulfene complexes [CpRu(mppe)(RHC/SO2)]PF6 (R = H, 2a; R = Me, 2b). Treatment of 2a with prochiral enamines or deprotonated β-oxo esters yielded C-C coupling products with 32-60% de. An analog of 2a, [NmcpRu(mppe)(H2C/SO2)]PF6 (8, Nmcp = neomenthylcyclopentadienyl) was prepared in a four-step synthesis starting from LiNmcp and [RuCl2(PPh3)3]. Repeated crystallization of the intermediate [NmcpRu(mppe)Cl] (6) provided diastereomerically pure 6′ which added methylene stereospecifically to give diastereomerically pure 8′. Compound 8 turned out to be much less reactive towards nucleophiles than 2a, but still added deprotonated ethyl 2-methyl-3-oxobutanoate with 44% de. The chiral, enantiomerically pure sulfur dioxide complex [CpRu(chir)(SO2)]PF6 [10, chir = (S,S)-Ph2PCHMeCHMePPh2] was synthesized from [CpRu(chir)Cl] and SO2 and was characterized by X-ray crystallography. Reaction of 10 with diazomethane gave the enantiomerically pure sulfene complex [CpRu(chir)(H2C/SO2)]PF6 (11). Addition reactions of 11 with N-(1-cyclopentenyl)morpholine, as well as with various enolates derived from β-oxo esters or 1,3-diesters proceeded with high yields and 20-90% de. The structure of a diastereomerically pure addition product, [CpRu(chir)(SO2CH2C(Me){C(O)Me}{C(O)OtBu}] (13d′), was determined crystallographically and was shown to have (R) configuration at the quaternary carbon atom. After alkylation of one of the S/O functions, the sulfinate ligand was cleaved from the metal center by ligand substitution with acetonitrile, and the resulting acetonitrile complex 15 was converted back into 10 by treatment with SO2.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 63
    Electronic Resource
    Electronic Resource
    Mixed Linear (M,Sb) Chains in the New Antimonides Hf10MδSb6-δ (M = V, Cr, Mn, Fe, Co, Ni, Cu): Crystal and Electronic Structures, Phase Ranges, and Electrical and Magnetic Properties (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 315-322 
    Details
    ISSN: 1434-1948
    Keywords: Metal-rich antimonides ; Magnetism ; Structure and bonding ; Conductivity ; LMTO ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title compounds can be synthesized in quantitative yields by arc-melting of stoichiometric amounts of HfSb2, Hf and one of the 3d metals V, Cr, Mn, Fe, Co, Ni, and Cu. These antimonides crystallize in a substitution variant of the W5Si3 type, in which one position is statistically mixed, occupied by the 3d metal atom M or the Sb2 atom in different ratios. Within the linear (M,Sb) chain, the M:Sb ratio may vary between 3:1 and 2:3. According to calculations of the electronic structures of Hf10MδSb6-δ with δ = 1, these phases are metallic compounds stabilized by strong Hf-Hf, Hf-M, and Hf-Sb bonds, and to a smaller extent by bonding interactions within the linear (M,Sb) chain. The metallic character was confirmed by measurements of the electrical resistivity and the magnetism of selected samples. Whereas Pauli paramagnetism was observed experimentally for M = V, Co, and Ni, Hf10FeSb5 is apparently the only phase with localized magnetic moments and magnetic coupling. This is in agreement with the magnetic ground state obtained solely for the ordered structure model of Hf10FeSb5 with spin-polarized calculation within the local spin density approximation.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 64
    Electronic Resource
    Electronic Resource
    A Two-Step Palladium-Catalyzed Coupling Scheme for the Synthesis of Ferrocene-Labeled Amino Acids (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 323-330 
    Details
    ISSN: 1434-1948
    Keywords: Amino acids ; Alkynes ; Ferrocene ; Palladium ; Catalysis ; Bioorganometallic chemistry ; Biosensors ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This work describes a Pd-catalyzed coupling of ferrocene alkyne derivatives to iodo amino acids. Ferrocene carboxylic acid propargyl amides were easily obtained in high yield. The crystal structures of the propargyl amine derivative 3 and the 1,1-diethylpropargylamine derivative 4 have been determined by X-ray diffraction. Pd-catalyzed coupling to p-iodoanilide amino acids gave the corresponding ferrocene-labeled amino acid derivatives, which were easily purified by diethyl ether extraction in the case of the 1,1-diethyl derivatives 8. The coupling reaction did not require anhydrous solvents and tolerated a variety of functional groups present in peptides such as alcohols (8a, Ser), thioethers (8d, Met), disulfide bonds (cystine, 12) esters (as in the N-labeled Leu derivative 10) and of course amides. A minor by-product of the coupling reaction, namely the homo-dimer bis(ferrocene carboxylic acid propargylamide) 9, was identified in the crude reaction mixtures by mass spectrometry and independently synthesized by oxidative coupling (Glaser and Eglington) of 3. All new compounds were completely characterized spectroscopically, including 15N- and 2D NMR spectroscopy, Mössbauer spectroscopy and electrochemistry. This work introduces a versatile procedure for a selective functionalization of amino acids with organometallics at the C-terminus which is expected to be of general applicability to peptide chemistry.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 65
    Electronic Resource
    Electronic Resource
    Potentially Tridentate Hydrazonic Ligands in the Synthesis of Methyl and Acetyl Palladium(II) Complexes (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 463-475 
    Details
    ISSN: 1434-1948
    Keywords: Palladium ; Insertion reactions ; Tridentate ligands ; Hydrazones ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Potentially tridentate hydrazonic ligands of the type HNNO have been used in the synthesis of some methyl palladium(II) complexes. Depending on the applied experimental conditions two different kinds of complexes are obtained. Thus, the reactions between HL1-HL5 and (COD)PdMeCl in diethyl ether led to the formation of bidentate methyl complexes of the type Pd(HNN)MeCl (1-5), where the ligands maintain a neutral character. However, in the presence of a base such as Et3N or NaOMe, the ligands are deprotonated with the consequent formation of tridentate methyl complexes of the type Pd(NNO)Me (7-10). In solution, complexes 1-5 tend to lose the hydrazonic proton with elimination of methane and formation of a tridentate chloride complex Pd(NNO)Cl (6); this tendency can be correlated with the acidity of the free ligands, which has been determined. On bubbling carbon monoxide through solutions of 1-5, the corresponding acetyl complexes Pd(HNN)[C(O)Me]Cl (11-15) are formed, in which both the cis and trans isomers are present. Their molar ratio is rationalised from the results of a molecular modelling study on the basis of electronic considerations. A remarkably different reactivity has been found in the carbonylation of the tridentate complexes 7-10: they decompose rapidly and quantitatively to palladium black and an organic product corresponding to the ligand with an acetyl group bonded to the hydrazonic nitrogen. The X-ray structures of a methyl complex (3) and its corresponding acetyl (13) derivative have been determined.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 66
    Electronic Resource
    Electronic Resource
    A Study of the Hydration and Dehydration of Vanadyl Arsenate by X-ray Diffraction Analysis, Infrared and Raman Spectroscopy (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 895-900 
    Details
    ISSN: 1434-1948
    Keywords: Vanadyl arsenate ; Hydrates ; Layered compounds ; Vibrational spectroscopy ; X-ray scattering ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The course of the intercalation and deintercalation of water molecules in vanadyl arsenate has been studied by X-ray diffraction analysis and by infrared and Raman spectroscopies. The formation of VOAsO4 hydrates at ambient temperature has been found to depend on relative humidity (r.h.): VOAsO4 · 5 H2O (basal spacing c = 10.48 Å) is formed at r.h. above 76%, VOAsO4 · 3 H2O (c = 8.03 Å) at 43-76% r.h., VOAsO4 · 2 H2O (c = 7.33 Å) at 11-43% r.h.; dehydrated VOAsO4 (c = 4.18 Å) exists near 0% r.h. Like the thermal dehydration of VOPO4 · 2 H2O, the thermal dehydration of VOAsO4 · 3 H2O proceeds in a stepwise manner so that the dihydrate and monohydrate are formed en route to the anhydrous compound. The arsenate monohydrate is gradually dehydrated over a broad temperature range. The broad diffraction lines observed can be explained in terms of the existence of a disordered phase containing monohydrated and anhydrous forms of vanadyl arsenate. A similar phenomenon has been observed during the dehydration of VOAsO4 · 3 H2O over phosphorus pentoxide at ambient temperature. The hydration of VOAsO4 is different from that of VOPO4. The first step, i.e. the insertion of water that coordinates to the vanadium atoms, is very slow. On the contrary, the uptake of further water molecules with the formation of higher hydrates is fast. It thus seems likely that the filling of one interlayer space with water facilitates the intercalation of further water into neighboring interlayer spaces. Therefore, only higher hydrates together with the original anhydrous phase are observed. Impedance spectral measurements indicate that the conductivity of the trihydrate has a mixed ionic/electronic character.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 67
    Electronic Resource
    Electronic Resource
    Preparation and Properties of Carbonyliron Complexes of 1-Aza-4-oxa-1,3-butadiene (α-Imino Ketone) - X-ray Crystal Structures of Fe(CO)3[MeN=C(Ph)C(Ph)=O] and Fe2(CO)4[tBuN=C(H)(Me)C(O)(O)C(Me)C(H)=NtBu] (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 907-919 
    Details
    ISSN: 1434-1948
    Keywords: Coordination chemistry ; α-Imino ketones ; CO complexes ; Iron complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of Fe2(CO)9 at room temperature in THF or toluene with the α-imino ketones R1N=C(R2)-C(R3)=O (L) (R1 = alkyl, R2 = H, Me, Ph, R3 = Me, Ph) (a-k), initially results in the formation of the mononuclear chelate Fe(CO)3(α-imino ketone) complexes 6 which can be isolated in moderate (6h) to high (6e-g) yield. Under these reaction conditions, complexes 6 subsequently react with [Fe(CO)4] fragments or dimerise, to form the dinuclear complexes Fe2(CO)6(α-imino ketone) (7a-j) or Fe2(CO)4(L-L) (8a,b,k), respectively. The complexes 8 contain two α-imino ketone ligands C-C coupled at the ketone carbon atoms. Complexes 8a,b react with CO at elevated temperatures to quantitatively yield Fe(CO)3(α-imino ketone) (6a,b). This reaction can be reversed photochemically. Irradiation of a solution of 6a,b in the low-energy band results in the reformation of 8a,b in almost quantitative yield. The extremely air-sensitive complexes 6 and the dinuclear complexes 7 and 8 have been characterised spectroscopically (IR, UV/Vis, 1H and 13C NMR) and by elemental analysis. The solid state structures of complexes 6g and 8a have been determined by single-crystal X-ray diffraction. The molecular structure of 6g confirms the flat σ-O,σ-N chelate coordination of the α-imino ketone. The structure of 8a consists of two metal-metal-bonded Fe(CO)2 units, bridged by a formally 10e-donating dianionic C-C coupled (tBu-ADO) ligand. A mechanism for the formation of complexes 8 is discussed.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99351_s.pdf or from the author.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 68
    Electronic Resource
    Electronic Resource
    Cationic ansa-(η5-Cyclopentadienyl)(η6-arene) Complexes of Titanium (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 929-932 
    Details
    ISSN: 1434-1948
    Keywords: Titanium ; Cyclopentadienes ; Arene complexes ; Cations ; Bridging ligands ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The half-sandwich titanium trimethyl complex (η5-C5H4CMe2Ar)TiMe3 (Ar = 3,5-Me2C6H3) reacts with the Lewis acid B(C6F5)3 to give the ionic TiIV ansa-cyclopentadienyl-arene complex [(η5,η6-C5H4CMe2Ar)TiMe2][MeB(C6F5)3]. In bromobenzene solvent, addition of more B(C6F5)3 leads to C6F5/Me exchange and, subsequently, to formation of an unusual dimeric TiIII dicationic species, {[(η5,η6-C5H4CMe2Ar)Ti(μ-Br)]2}[B(C6F5)4]2, which was structurally characterized. Its formation involves reduction of the transition-metal center, solvent C-Br cleavage and perfluoroaryl-group scrambling.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99383_s.pdf or from the author.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 69
    Electronic Resource
    Electronic Resource
    On the Hydrolysis of tBu2Ge(OEt)2: Supramolecular Self Assembly in the Solid State of 2 tBu2Ge(OH)2, (tBu2GeOH)2O, and H2O (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 939-941 
    Details
    ISSN: 1434-1948
    Keywords: Germanium ; Germanol ; Hydrogen bonds ; X-ray structure ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hydrolysis of tBu2Ge(OEt)2 is described. Depending on the amount of water used either tBu2Ge(OH)2 (1) or a mixture of the latter and (tBu2GeOH)2O (2) were obtained. A cocrystallate consisting of 2tBu2Ge(OH)2, (tBu2GeOH)2O and water was the subject of a single crystal X-ray diffraction study. In the solid state the individual molecules are connected by hydrogen bonds giving rise to the formation of a polymeric double chain ribbon.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 70
    Electronic Resource
    Electronic Resource
    Inclusion of Copper(I) into a Novel Bipyridine-Containing Tetraphosphadiplatinacyclophane (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 959-969 
    Details
    ISSN: 1434-1948
    Keywords: Bipyridyldiphosphane ligands ; Macrocycles ; Metallacyclophanes ; Platinum ; Supramolecular chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 5,5′-bis(hydroxyalkyl)-2,2′-bipyridines 4a-c (Scheme 1) were prepared either in one step (4b, 4c) or in four steps (4a) starting with 5,5′-dimethyl-2,2′-bipyridine in each case. Reaction of 4a-c with mesyl chloride afforded the bis(mesylates) [-C5H3N-(CH2)n-CH2-OSO2Me]2 5a-c [n = 1 (a), 2 (b), 3 (c)], which could easily be transformed into the diphosphanes 6a-c by reaction with LiPPh2. Treatment of 6c, 6b with Cl2Pt(NCPh)2 and (RC6H4)2Pt(COD) according to the high-dilution method resulted in the formation of the tetraphosphadiplatinacyclophanes [-C5H3N-(CH2)4-PPh2PtCl2PPh2-(CH2)4-C5H3N-]2 (7c) and [-C5H3N-(CH2)3-PPh2Pt(C6H4R)2PPh2-(CH2)3-C5H3N-]2 (8b, 9b) (8b: R = H, 9b: R = tBu), respectively (Scheme 2). The molecular structures of 8b and 9b were elucidated by X-ray structural analyses. The noncoordinated bipyridine moieties in 8b were employed to encapsulate copper(I) to give the host/guest complex 10b (Scheme 3), which was investigated by FAB-MS, NMR spectroscopy, and cyclovoltammetry. 10b exhibited a quasi-reversible oxidation at E1/2 = -0.31 V and an electrodeposition-redissolution redox system at E1/2 = -0.79 V, owing to the formation of copper at the surface of the working electrode.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 71
    Electronic Resource
    Electronic Resource
    Experimental Evidence for a Second Coordination Sphere Water Molecule in the Hydration Structure of YbDTPA - Insights for a Re-Assessment of the Relaxivity Data of GdDTPA (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 971-977 
    Details
    ISSN: 1434-1948
    Keywords: Lanthanides ; Ytterbium ; MRI contrast agents ; Solid-state structures ; Hydration ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The low temperature (-100 °C) X-ray structure of the complex K2[Yb(DTPA)(H2O)] has been determined. The metal ion is at the center of a tricapped trigonal prism and is nine-coordinate, binding to the three nitrogens and five oxygens of the ligand and one water molecule. From the structure obtained, three well-defined hydration shells can be observed consisting of: i) one coordinated water molecule; ii) several water molecules in the outer coordination sphere of the YbIII ion and iii) one water molecule surprisingly close to the metal center and hydrogen-bonded to proximate carboxylate groups. A variable-field and temperature NMRD study of the corresponding Gd complex has been performed and the data interpreted by taking into account the presence of second-sphere water molecule(s). The results of the analysis are in excellent agreement with the X-ray structural data.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 72
    Electronic Resource
    Electronic Resource
    New Insights into the Mechanism of Hydroperoxide Activation by Investigation of Dynamic Processes in the Coordination Sphere of Seven-Coordinated Molybdenum Peroxo Complexes (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 1107-1114 
    Details
    ISSN: 1434-1948
    Keywords: Catalysis ; Densitiy functional theory ; Epoxidation ; Reaction mechanisms ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Seven-coordinated molybdenum oxobisperoxo complexes with chelate nitrogen donors like pyrazolylpyridines are catalysts for the epoxidation of olefins. An NMR spectroscopic and quantumchemical study on the fluxionality of the chelate ligand proves that during this process partial ligand dissociation takes place. This gave rise to a detailed theoretical study on the activation of CH3OOH at the model complex (NH3)2MoO(O2)2 including dissociation of one of the ammonia ligands and proton transfer from the hydroperoxide to one of the peroxo ligands.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99429_s.pdf or from the author.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 73
    Electronic Resource
    Electronic Resource
    Tripodal Oxygen Ligand Supported Palladium(II) Complexes: Alkylation, Carboxymethylation, and CO Insertion Reactions - X-ray Crystal Structure Determination of [PdL2], L- = [(C5H5)Co{P(O)(OMe)2}3]-, a Novel Homoleptic Oxygen Ligand Palladium Complex (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 21-28 
    Details
    ISSN: 1434-1948
    Keywords: Palladium ; Tripodal ligands ; O ligands ; Fluxionality ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of [PdCl2(CH3CN)2] with the silver salt of the tripodal oxygen ligand L- = [(C5H5)Co{P(O)(OMe)2)}3]- yields the homoleptic oxygen ligand complex [PdL2] (1). The molecular structure of 1 was determined by single-crystal X-ray diffraction: monoclinic space group P21/n; a = 8.515(1), b = 13.627(2), c = 15.828(2) Å; β = 92.44(1)°; V = 1834.9(7) Å3; Z = 2. The complexes [Pd(PPh3)XL] [X = Cl (2a), Br (2b), I (2c)] have been prepared starting from 1. Complex 2a reacts with PPh3 to form [Pd(PPh3)2L]Cl (3a) and [Pd(PPh3)2L]L (3b). Treatment of 2a with CO in MeOH yields the carboxymethyl complex [{(PPh3)(COOMe)Pd(μ-Cl)}2] (4) and the protonated ligand HL. The carboxymethyl complex 4 shows some catalytic activity for the copolymerization of CO and ethene. Complex 4 reacts with AgL to yield [Pd(PPh3)(COOMe)L] (6). Alkylation of 2a with Me4Sn leads to the methyl complexes [Pd(PPh3)MeL] (7) and [Me2ClSnL] (8). CO insertion in the palladium-carbon bond of 7 gives the stable acetyl complex [Pd(PPh3){C(O)Me}L] (10). The palladium(II) complexes 1, 2, 3, 6, 7, and 10 of the tripodal oxygen ligand L are all fluxional molecules that have been studied by temperature-dependent 1H- and 31P-NMR spectroscopy.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 74
    Electronic Resource
    Electronic Resource
    Neopentane-Based Tripodal CpL2 Ligands: Synthesis and Reactions of CH3C(CH2-η5-C5H4)(CH2-η1-PPh2)2RuCl; Hindered Rotation of Vinylidene Ligands (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 33-50 
    Details
    ISSN: 1434-1948
    Keywords: Tripod ligands ; Hindered rotation of vinylidene ligands ; CpML2 chelate ligands ; Ruthenium ; Carbenes ; Carbene-type ligands ; Cyclic voltammetry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tripodal ligand [CH3C(CH2C5H4)(CH2PPh2)2]- reacts with RuCl2(PPh3)3 to produce CH3C(CH2-η5-C5H4)(CH2-η1-PPh2)2RuCl, [tripodCpL2RuCl], 1. Complex 1 undergoes substitution of the chlorine function with various nucleophiles L′ to produce [tripodCpL2RuL′]+. The carbonyl derivative (L′ = CO) 2, isonitrile (L′ = RNC) 3, nitrile compounds (L′ = RCN) 4, and a tolane adduct (L′ = η2-PhC≡CPh) 5 are obtained when 1 is treated with the appropriate ligands in polar solvents. Halide acceptors (e.g. TlPF6) are generally needed to promote these reactions. The cyanide derivative tripodCpL2RuCN (3a) is alkylated by F3CSO3CH3 to give the isonitrile derivative [tripodCpL2RuCNMe]+3b. Terminal alkynes HC≡CR produce vinylidene compounds [tripodCpL2RuL′]+, where L′ = C=CHR (R = tBu, 7b; R = Ph, 7c), or allenylidene derivatives, L′ = C=C=CPh2 (6), depending on the nature of R (R = CPh2OH for synthesis of 6). Trimethylsilylacetylene gives the parent vinylidene species, L′ = C=CH2 (7a), which is transformed to the Fischer-type carbene compound, L′ = C(OMe)Me (8), upon treatment with methanol. The vinylidene species 7 are deprotonated by NaOMe to produce the alkynyl compounds tripodCpL2RuC≡CR (9). Methylation of 9 with F3CSO3CH3 results in the vinylidene derivatives L′ = C=C(Me)R (R = tBu, 7d; R = Ph, 7e), having two organic substituents at the terminal carbon centre. For all vinylidene compounds with two different substituents at their terminal carbon atom, hindered rotation of the single-faced vinylidene π-ligand about its Ru-C bond is observed. Analysis by 31P-NMR spectroscopic coalescence measurements as well as line-shape analyses reveals activation enthalpies of around 40 kJmol-1 for this rotation, with small activation entropies of around ±10 Jmol-1K-1. Solid-state structures of nine compounds of the type [tripodCpL2RuL′]+n (n = 0, 1) demonstrate the remarkable conformational rigidity of the tripodCpL2Ru template. They also show that the possible strain imposed by linking the Cp ligand and the two donor groups L in one and the same chelate scaffolding does not appear to impose a serious steric strain on these templates.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 75
    Electronic Resource
    Electronic Resource
    Syntheses and Coordination Chemistry of Chiral Phosphanyl Glycerols and Their Derivatives - X-ray Structure of (R)-Ph2P-CH2-CaH-O-B(Ph)-O-CbH2(Ca-Cb) (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 65-73 
    Details
    ISSN: 1434-1948
    Keywords: (R)-(+)-2,3-Epoxy-1-propanol ; 2,3-Dihydroxyalkyl phosphanes ; 1,3,2-Dioxaborolane ; 1,3-Dioxolane ring ; Enantiopure phosphanes ; Complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of (R)-(+)-2,3-epoxy-1-propanol with Ph2PH, Ph(Me)PH, or PhPH2 in the superbasic medium KOH/DMSO affords the novel chiral phosphanes 1a-1c. While 1a is obtained enantiomerically pure, 1b and the secondary phosphane 1c are formed as mixtures of diastereoisomers (RPRC, SPRC) with homochiral β carbon atoms. Derivatization of 1a with phenylboronic acid or 2,2-dimethoxypropane yields 2a and 3a with 1,3,2-dioxaborolane and 1,3-dioxolane ring systems, respectively. The X-ray structure of 2a (space group P21) reveals the presence of four molecules of R configuration in the unit cell. Nucleophilic phosphanylation of (R)-(-)-2,3-O-isopropylideneglycerol tosylate with Ph2PH, Ph(Me)PH, or PhPH2 yields chiral 3a-3d. Compound 3b was obtained enantiomerically pure. The secondary phosphane 3c has been employed in syntheses of the hydrophilic tertiary phosphanes 3e, 3f and of the novel bidentate phosphane ligands 3g, 3h, all of which have homochiral β carbon atoms. PdII complexes PdL2Cl2 of 1a, 2a, 3a (L) are formed as mixtures of cis/trans isomers. RhI complexes of 1a, 3a, and bidentate 3h have also been synthesized.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 76
    Electronic Resource
    Electronic Resource
    Controlled Thiolate Coordination and Redox Chemistry: Synthesis, Structure, Axial-Binding, and Electrochemistry of Dinickel(II) Dithiolate Macrocyclic Complexes (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 169-179 
    Details
    ISSN: 1434-1948
    Keywords: Macrocycles ; Nickel ; Redox chemistry ; Schiff bases ; S ligands ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A single crystal X-ray analysis of [Ni2L1](ClO4)2· MeCN · 1/4 H2O, 1a [formed directly from a mixture of nickel(II) template ions, 2,6-diformyl-4-methyl-thiophenolate, and 1,4-diaminobutane] reveals that the nickel(II) ions are in square-planar N2S2 environments and that the four “bowed” dinickel macrocycles in the asymmetric unit pack around a single central perchlorate template ion encapsulating it to form “star” clusters of stoichiometry {[Ni2L1]4(ClO4)}7+. These “stars” stack together, via π-π-stacking interactions, to form two-dimensional sheets, which are separated from one another by layers of the remaining perchlorate anions and solvent molecules. Reduction, by NaBH4, of the four imine bonds in [Ni2L2](ClO4)22a (analogous to 1a but formed from 1,3-diaminopropane not 1,4-diaminobutane) or [Ni2L2](CF3SO3)22b to amine bonds produces the corresponding tetra-amine complex, [Ni2L3](ClO4)23. These complexes are shown to contain diamagnetic nickel(II) ions by a combination of magnetic, NMR and UV/Vis spectroscopic results. The 1H NMR spectra of 1-3 run in [D3]MeNO2 and in [D3]MeCN are consistent with increasing axial binding ability in the order: 3 〈 2 〈 1. Thiocyanate ion binding studies reveal that 1 and 2 are able to coordinate two thiocyanate ions, forming [Ni2L1(NCS)2] 4 and [Ni2L2(NCS)2] 5 respectively, whereas 3 does not. Single crystal X-ray analyses of complexes 4· 2 MeCN and 5· MeCN show that adjacent square-planar and octahedral nickel(II) ions result. Two one-electron oxidations and two one-electron reductions are a feature of the electrochemistry of 1-3 in MeCN: curiously, the potentials for the oxidation processes are almost invariant whereas those for the reduction processes vary as anticipated. EPR spectroscopy shows that the first one-electron reduction process and the first one-electron oxidation process are metal centred. Spectroelectrochemical studies and redox titrations indicate that a purplish-coloured complex is produced by one-electron oxidation of 2 (λ = 870 nm, ε = 1320 L mol cm-1). The synthesis of a phenolate analogue, [Ni2L′(MeCN)4](ClO4)2 (6), of the thiophenolate complex 2a is also detailed. Complex 6 undergoes two one-electron oxidations in MeCN, but, in contrast to the thiophenolate complexes 1-3, these occur at much higher potentials. Only a single one-electron reduction process is observed and this occurs at a more negative potential than for any of 1-3.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 77
    Electronic Resource
    Electronic Resource
    Synthesis, Crystal Structures, and Solution Properties of N-Methylene(phenyl)phosphinic Acid Derivatives of Cyclen and Cyclam (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 195-203 
    Details
    ISSN: 1434-1948
    Keywords: Acid derivatives ; Cyclen and cyclam derivatives ; Phosphinic acid ; Potentiometry ; Protonation and stability constants ; 31P-NMR titration ; Hydrogen bonding ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two phenylphosphinic acid derivatives of tetraaza macrocycles, (1,4,7,10-tetraazacyclododecanetetrayl)tetrakis(methylene)tetrakis(phenylphosphinic acid) [(H4L1) and (1,4,8,11-tetraazacyclotetradecanetetrayl)tetrakis(methylene)tetrakis(phenylphosphinic acid)] (H4L2), were synthesised and the crystal structures of H4L2 and its bis(1-adamantylammonium) salt were determined. In both the structures, the ring conformation is virtually the same and is stabilised by hydrogen bonds. Protonation constants of the acids and stability constants of their Zn2+ and Cd2+ complexes were determined pH-metrically at 25 °C and at an ionic strength of 0.1 mol dm-3 (KNO3). The pKA values found for both the compounds are lower than those for their carboxylic analogues and correspond to the expected electron-withdrawing ability of the -P(Ph)O2H moiety. The value pK1 of the last dissociation constant of H4L1 is surprisingly high. The complexes of Zn2+ and Cd2+ with (L1)4- and (L2)4- are less stable than those with other similar ligands, which is in accordance with lower overall basicity of H4L1 and H4L2. A pronounced drop in the stability of the complexes of H4L2 can be explained by partial coordination of the ligand to the metal ions. The solution properties of the ligands were also investigated by 31P-NMR spectroscopy. The spectra observed suggest stable (on the NMR time scale) conformations of the protonated ligands in solution. A comparison of NMR spectra in solution and CP/MAS-NMR spectra indicates that the structures of the conformers roughly correspond to the structures observed in the solid state. The conformations are stabilised by intramolecular hydrogen bonds and by hydrophobic interactions of phenylphosphinic moieties. The conformers are stable even at 90 °C, but not in the presence of complexing metal ions.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99149_s.pdf or from the author.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 78
    Electronic Resource
    Electronic Resource
    Synthesis, Spectroscopic, and Electrochemical Properties of Rare Earth Double-Deckers with Tetra(tert-butyl)-2,3-naphthalocyaninato Ligands (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 205-209 
    Details
    ISSN: 1434-1948
    Keywords: Rare earth complexes ; Naphthalocyaninato ligand ; Double-decker complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of rare earth(III) double-deckers RE[Nc(tBu)4]2 [RE = La, Ce, Pr, Nd, Eu, Gd, Tb, Y, Er; Nc(tBu)4 = dianion of tetra(tert-butyl)-2,3-naphthalocyanine] (1-9) have been prepared by treating RE(acac)3·n H2O (acac = acetylacetonate) with 6-tert-butylnaphthalonitrile in refluxing n-octanol in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). These novel sandwich-type complexes have been spectroscopically characterized. The electrochemical studies show that the first oxidation and the first reduction potentials increase with the size of the central metal ions with a relatively small separation (0.28-0.33 V), reflecting the narrow HOMO-LUMO gap.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 79
    Electronic Resource
    Electronic Resource
    Dipolar and Non-Dipolar Pyridine and Bipyridine Metal Complexes for Nonlinear Optics (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 229-239 
    Details
    ISSN: 1434-1948
    Keywords: Pyridine derivatives ; Bipyridine derivatives/Metal complexes ; Chromophores ; Nonlinear optics ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metal complexes of pyridine and bipyridine-type ligands represent an important class of nonlinear optical (NLO) materials: (i) They can incorporate a variety of functionalised ligands with a wide range of metals which can give rise to tuneable NLO properties; (ii) they are generally associated with intense low-lying charge-transfer excitations such as metal to ligand charge-transfer (MLCT) or intraligand charge-transfer (ILCT); (iii) bipyridyl ligands are also good building blocks that allow the construction of octupolar complexes with a defined geometry and symmetry. This review describes the recent developments in the design of such dipolar and octupolar chromophores for second-order nonlinear optics.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 80
    Electronic Resource
    Electronic Resource
    Reactivity of Silyl-Substituted Heterobimetallic Iron-Platinum Hydride Complexes towards Unsaturated Molecules, I Alkyne Insertions into the Platinum-Hydride Bond, Phosphane-Induced σ-Alkenyl-μ-Vinylidene Rearrangements and Formation of μ-Isonitrile Complexes (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 241-252 
    Details
    ISSN: 1434-1948
    Keywords: Heterobimetallics ; Hydride complexes ; Alkenyl complexes ; μ-Isonitrile complexes ; Silicon ; Iron ; Platinum ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The heterobimetallic hydride complexes [(OC)3Fe{Si(OMe)3}(μ-Ph2PXPPh2)Pt(H)(PR3)] (1a: X = CH2, PR3 = PPh3; 1b: X = NH, PR3 = PPh3; 1c: X = CH2, PR3 = PMePh2) have been prepared by the oxidative addition of [(OC)3Fe(H){Si(OMe)3}(η1-Ph2PXPPh2)] to [Pt(H2C=CH2)(PPh3)2] or by reaction of K[(OC)3Fe{Si(OMe)3}(η1-dppm)] with trans-[Pt(Cl)(H)(PPh3)2]. The solid-state structure of compound 1b has been determined by single-crystal X-ray diffraction. 1-Alkynes such as methylpropiolate or phenylacetylene insert in a regiospecific manner into the Pt-H bond of 1 to yield the σ-alkenyl complexes [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-Ph2PXPPh2)Pt{C(R)=CH2}] (2a: X = CH2, R = CO2Me; 2b: X = NH, R = CO2Me; 3a: X = CH2, R = Ph). Addition of the Pt-H bond of 3a across the triple bond of [D1]phenylacetylene affords [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppm)Pt{C(Ph)=C(D)H}] (3a*) having the deuteron trans to platinum (cis addition). This insertion reaction is accompanied by dissociation of the platinum-bonded PR3 ligand and saturation of the vacant coordination site by a dative μ-η2-Si-O→Pt interaction. When 3 is treated with PR3 again, a subsequent phosphane-induced rearrangement leading to vinylidene-bridged complexes [(OC)3Fe{μ-C=C(H)R′}(μ-Ph2PXPPh2)Pt(PR3)] (4a: X = CH2, R′ = Ph, PR3 = PPh3; 4b: X = NH, R′ = Ph, PR3 = PPh3; 4c: X = CH2, R′ = Ph, PR3 = PMePh2; 4d: X = CH2, R′ = p-tolyl, PR3 = PPh3) occurs. Upon purging a solution of 3a with carbon monoxide, the labile CO adduct [(OC)3Fe{Si(OMe)3}(μ-dppm)-Pt(CO){C(Ph)=CH2}] 5a is formed, addition of 2,6-xylyl isocyanide to 2a and 3a affords the isonitrile adducts [(OC)3Fe{Si(OMe)3}(μ-dppm)Pt(CNxylyl){C(R)=CH2}] (5b: R = CO2Me; 5c: R = Ph), respectively. When hydride complex 1a is allowed to react with stoichiometric amounts of aromatic isonitriles, formal elimination of HSi(OMe)3 occurs, yielding the heterodinuclear isonitrile-bridged complexes [(OC)3Fe(μ-C=N-R)(μ-dppm)Pt(PPh3)] (6a: R = 2,6-xylyl; 6b: R = o-anisyl; 6c: R = p-anisyl; 6d: R = p-C6H4NH2) and the bis(isonitrile) complexes [(OC)2(RN≡C)Fe(μ-C=N-R)(μ-dppm)Pt(PPh3)] (7a: R = 2,6-xylyl; 7b: R = p-anisyl). Single-crystal X-ray diffraction studies perfomed on 6a and 6b reveal that the molecular structures of these μ-isonitrile complexes closely resemble the μ-vinylidene complexes 4. The two metal centers are bridged in a symmetric manner by strongly bent CNR ligands, the aromatic groups R being oriented towards the Fe(CO)3 moiety. Electrophilic addition of HBF4 to the basic nitrogen atom of the μ-CNR ligand transforms 6 to the cationic μ-aminocarbyne complexes [(OC)3Fe{μ-CN(H)R}(μ-dppm)Pt(PPh3)][BF4] (8a: R = 2,6-xylyl; 8b: R = p-anisyl; 8c: R = p-C6H4NH2).
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 81
    Electronic Resource
    Electronic Resource
    “Crowned” Fe4S4 Clusters as Electrochemical Metal Ion Sensors (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 253-264 
    Details
    ISSN: 1434-1948
    Keywords: Iron-sulfur clusters ; Crown ethers ; Electrochemical devices ; Host-guest chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of Fe4S4 cluster compounds, I, III, and V, in which the cuboidal cluster core is appended with four crown ether thiolate ligands, and II and IV, bearing thiolate ligands without crown ether parts, has been synthesized and characterized. The spectroscopic and electrochemical properties of these compounds are determined by the electronic nature of the thiolate ligands. Only in the case of III, where a very short α-thioacetyl linker was used to connect the crown ether ligands to the cluster core, was a restricted conformational freedom of the ligand observed. A detailed electrochemical study of the influence of alkali and earth alkali metal ions (Li+, Na+, K+, Mg2+, and Ba2+) on the reversible 2-/3- reduction of the cluster compounds was performed. In the case of the crown ether appended clusters I, III, and V, the addition of these metal ions resulted in an anodic shift, i.e. in positive direction, of the reduction potential (modulation effect) and to larger current responses (promotion effect). The magnitude of the modulation effects is determined by the binding affinity of the metal ions in the crown ether ligands, and by the distance between bound metal ions and the redox active cluster core. Variation of the linker between the cluster core and the metal ion binding site resulted in cluster compounds with almost inverse selectivities for e.g. K+ and Ba2+ in the case of I and III. For the large effects found for compound I a lariat binding mode is proposed.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 82
    Electronic Resource
    Electronic Resource
    Aluminium Coordinations in Zeolite Mordenite By 27Al Multiple Quantum MAS NMR Spectroscopy (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 281-285 
    Details
    ISSN: 1434-1948
    Keywords: NMR spectroscopy ; Zeolites ; Al-coordination ; Mordenite ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 27Al 3Q MAS NMR spectroscopy has been applied to study the coordination state of the species giving the 30 ppm Al NMR signal in the 27Al MAS NMR spectrum of activated mordenite materials. From the 27Al 3Q MAS NMR measurements it is evident that the broad peak at 30 ppm in the 27Al NMR spectrum of the mordenite calcined at temperatures up to 600 °C comes mainly from the distorted four-coordinated Al. By simulation a quadrupolar coupling constant of 5.8 MHz was estimated for the distorted tetrahedral Al. For samples calcined at 650 and 700 °C, a small amount of pentacoordinated Al emerges. The majority of the signal, however, arises from distorted tetrahedral Al. A two-step calcination results in a significant contribution of the pentacoordinated Al to the signal at 30 ppm. From the simulated line-shape, a quadrupole coupling constant of 6.2 MHz is obtained for the latter signal. These data show that during the calcination of the mordenite, the coordination environment at the Al centre gradually becomes distorted to give rise to the shoulder at 30 ppm. With the increase of the calcination temperature, pentacoordinated Al species form
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 83
    Electronic Resource
    Electronic Resource
    Synthesis, Crystal Structure, Spectroscopic and Magnetic Properties of an Unprecedented Three-Dimensional CuII Coordination Compound of 1,2-Bis(1,2,4-triazol-4-yl)ethane (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 307-314 
    Details
    ISSN: 1434-1948
    Keywords: Copper ; Magnetic properties ; Supramolecular chemistry ; Three-dimensional architecture ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel three-dimensional copper(II) compound of the formula [Cu3(btre)5(H2O)2](ClO4)6·H2O (btre = 1,2-bis(1,2,4-triazol-4-yl)ethane) has been synthesized. The structure has been solved at 150 K by single-crystal X-ray analysis. The compound [C30H44Cu3N30O2·6(ClO4)·H2O] crystallizes in the triclinic space group P1bar with a = 12.488(1), b = 13.195(1), c = 19.756(2) Å, α = 78.959(8), β = 84.553(8), γ = 63.869(7)°, V = 2868.4(5) Å3, Z = 2 (trinuclear CuII units), 6484 reflections [I 〉 4σ(Ι)], RF = 0.0581, wR2 = 0.1214. The structure of this coordination polymer consists of a three-dimensional network built up from linear trinuclear CuII cations of formula [Cu3(btre)5(H2O)2]6+. This crystallographically independent unit comprises a linear array of three CuII ions linked by triple N1,N2-1,2,4-triazole bridges, yielding Cu1-Cu2 = 3.893(1) Å and Cu2-Cu3 = 3.889(1) Å. These linear trinuclear CuII units are linked by various pathways involving tridentate and tetradentate bridging btre ligands, which yields an unprecedented three-dimensional network. The CuII ions are weakly antiferromagnetically coupled with J = -1.01(2) cm-1 (based on the Hamiltonian: H = -J[SCu1·SCu2 + SCu2·SCu3] using the expression for the molar magnetic susceptibility S = 1/2 of a linear trinuclear system). The nature and the magnitude of the antiferromagnetic exchange have been discussed on the basis of the structural features.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 84
    Electronic Resource
    Electronic Resource
    Mono and Dinuclear Tungsten Alkenyl-Carbyne Complexes Bridged by Cyanide and Diisocyanide Ligands: Synthesis, Electrochemical- and 183W-NMR Studies (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 341-350 
    Details
    ISSN: 1434-1948
    Keywords: Alkenylcarbynes ; Dinuclear tungsten complexes ; Electrochemistry ; Tungsten NMR ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Neutral trans-cyanide alkenylcarbyne complexes 2a and 2b have been prepared by reaction of the complex 1a and 1b with NaCN or [Bu4N]CN. The reaction of complexes 2a and 2b with an equimolar amount of the acetonitrile complexes 1a and 1b in CH2Cl2 leads to the cationic cyanide-bridged bis(alkenylcarbyne) di-tungsten complexes 3a-d. Diisocyanide-bridged bis(alkenylcarbyne) di-tungsten complexes 4a and 4b have been synthesized by the reaction of complexes 1a and 1b with 0.5 equivalents of the diisocyanide 1,4-(CN)2C6H4. IR as well as 1H-, 31P{1H}-, 13C{1H}-, and 183W-NMR data are reported. The spectroscopic data show that in the dinuclear complexes 3a-d, the bridging CN group and the alkenylcarbyne units are located in trans positions, while in the dinuclear complexes 4a and b, the isocyanide groups of the bridging ligand 1,4-(CN)2C6H4 and the two alkenylcarbyne moieties are cis. The 183W chemical shifts of complexes 2a, 2b, 3a-d, 4a, and 4b were obtained through two-dimensional indirect 31P, 183W NMR recording techniques. A downfield shifting of 183W resonances of the cyanide-bridged dinuclear complexes 3a-d with respect to the mononuclear ones, 2a and 2b, was observed. The δ183W of isocyanide bridging dinuclear complexes 4a and 4b appear at higher field than those of the corresponding mononuclear cyanide 2a and 2b in accordance with the higher π-acceptor electron properties of the isocyanide ligand. The electrochemical behaviour of all the complexes has been investigated by cyclic voltammetry and controlled potential electrolysis in aprotic media and at a Pt (or vitreous C) electrode. Complexes 1, 2, or 3 undergo multi-electron irreversible oxidation processes involving anodically induced proton dissociation from the alkenylcarbyne ligands, and irreversible cathodic processes are also observed for all the complexes. The order of the redox potentials reflects that of the net electron π-acceptor/σ-donor character of the ligands and the ligating alkenylcarbynes are shown to behave as remarkably strong π-electron acceptors (even stronger than CO).
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 85
    Electronic Resource
    Electronic Resource
    An SiO2-Embedded Nanoscopic Pd/Au Alloy Colloid (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 819-822 
    Details
    ISSN: 1434-1948
    Keywords: Colloids ; Sol-gel processes ; Immobilization ; Heterogeneous catalysts ; Hydrogenations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A bimetallic, fully alloyed Pd/Au colloid of 3.0 nm particle size, obtained by the co-reduction of Pd and Au salts with tetraalkylammonium triethylhydroborate, was embedded in a silica matrix employing a modified sol-gel procedure with THF as the solvent. The removal of the protecting tenside led to a mesoporous texture with a comparatively narrow pore distribution. The physical characterisation by a combination of several techniques has shown that the SiO2-embedded Pd/Au colloid preserves the size and the structural characteristics of the colloidal metal precursor. The new material exhibits catalytic properties in selective hydrogenation.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 86
    Electronic Resource
    Electronic Resource
    Linear, Divergent Molecular Receptors - Subtle Effects of Transition Metal Coordination Geometry (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 823-826 
    Details
    ISSN: 1434-1948
    Keywords: Thiacalixarene ; Trimetallic sandwich ; Cobalt ; Zinc ; Divergent receptors ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction between deprotonated p-tert-butyltetrathiacalix[4]arene and CoII or ZnII under strictly defined conditions leads to the formation of sandwich species in which a trimetallic unit is held between two opposed, divergently oriented, staggered O- and S-bound calixarene ligands in the cone conformation. Despite the isomorphous nature of the crystalline compounds, there is a subtle difference in the coordination of CoII and ZnII, presumably related to the differences in metal radius and electron configuration combined with structural restrictions imposed by the calixarene framework, in that whereas all three Co atoms may be considered six-coordinate (and approximately octahedral), only two of the Zn atoms appear so, the third being five-coordinate and more nearly trigonal bipyramidal in its coordination geometry.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 87
    Electronic Resource
    Electronic Resource
    Coordination Chemistry of Calix-Phosphanes: Cooperativity in the Assembly of a Tetragold Calixarene Complex (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 831-834 
    Details
    ISSN: 1434-1948
    Keywords: Metallo-calixarenes ; Gold complexes ; Tetraphosphane ; Stability constants ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Assemblage of the tetragold complex [L·(AuCl)4] from p-tert-butyl-calix[4]-(OCH2PPh2)4 (L) and [AuCl(tetrahydrothiophene)] was investigated by NMR and UV/Visible spectroscopic titrations. Three steps could be resolved and are assigned, respectively, to addition of one, two and four AuCl units to the macrocyclic ligand. At each stage of metallation, symmetrical species persist on the NMR time scale since the bound AuCl fragments migrate between the different phosphorus centers via both intra- and intermolecular processes. The derived stability constants (logβ1 = 4.4 ± 0.2, logβ2 = 7.0 ± 0.7, and logβ4 = 14.5 ± 2.0) indicate both positive and negative cooperativity during build-up of the tetranuclear species. An X-ray diffraction study made with crystals obtained from an L:Au (1:2) mixture revealed the formation of an unusual binuclear complex whose solid state structure comprises a polymeric chain of [L·AuCl] units linked by pseudo-tetrahedral Au+ ions, each generic unit containing a pendant linear PAuCl fragment. This polymeric species, with its two distinct binding modes, provides a simple rationale by which to explain the role of cooperativity in the overall assembly process.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 88
    Electronic Resource
    Electronic Resource
    Alkyne[hydrotris(pyrazolyl)borato]tantalum Complexes - An Ethyl Group is a Better α-Agostic Donor Than a Methyl Group (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 839-842 
    Details
    ISSN: 1434-1948
    Keywords: Tris(pyrazolyl)borate ; Tantalum ; Agostic interactions ; Alkyne complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of unprecedented alkyne hydrotris(3,5-dimethylpyrazolyl)borato (TpMe2) tantalum(III) complexes is reported. The parent dichloro complex TpMe2TaCl2(PhC≡ CCH3) (2) is obtained from TaCl3(DME)(PhC≡CCH3) and KTpMe2. 2 reacts with methyllithium to give the dimethyl complex TpMe2Ta(CH3)2(PhC≡CCH3) (3) and with ethylmagnesium chloride to give the X-ray characterized α-agostic ethyl complex TpMe2Ta(Cl)(μ-H-CHCH3)(PhC≡CCH3) (4). Reaction of 4 with methyllithium generates the mixed methyl ethyl complex TpMe2Ta(CH3)(μ-H-CHCH3)(PhC≡CCH3) (5) in solution. Spectroscopic data indicate that 5 is α-agostic at the ethyl group only.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 89
    Electronic Resource
    Electronic Resource
    Preparation of Organic Polysulfanes R2Sn (n = 5, 7, 8, 9) from Sulfenyl Chlorides, RSCl, and Transition Metal Polysulfido Complexes (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 921-928 
    Details
    ISSN: 1434-1948
    Keywords: Sulfur ; Titanium ; Zinc ; Polysulfido complexes ; Sulfur heterocycles ; Polysulfides ; Polysulfanes ; Sulfenyl chlorides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation of seven novel organic polysulfanes is reported. Bis(n-octyl)heptasulfane R2S7 1 is formed upon reaction of RSCl with [Cp2TiS5], while the corresponding nonasulfane R2S9 2 is obtained by reaction of RSSCl with [Cp2TiS5]. The bis(n-octyl)pentasulfane R2S5 3 is obtained from RSCl and [(Cp′2TiCl)2S3] by transfer of the S3 ligand at 20 °C. The new alkyl polysulfanes 1-3 have been obtained in quantitative yields. They are liquids at 20 °C, having freezing points below -50 °C, but do not form mesogenic phases. Reactions of [Cp2TiS5] with 2-naphthyl- and 4-chlorophenyl sulfenyl chloride furnish the corresponding heptasulfanes 4 and 5, respectively, which are solids at 20 °C. 1,2-Benzodisulfenyl chloride C6H4(SCl)2 reacts with [(Cp′2TiCl)2S3] to give the known 1,2,3,4,5-benzopentathiepin C6H4S5 6, with [Cp2TiS5] to give the novel 1,2,3,4,5,6,7-benzoheptathionin C6H4S7 7, and with [(TMEDA)ZnS6] to give the novel 1,2,3,4,5,6,7,8-benzooctathiecin C6H4S8 8. The cyclic polysulfanes 6-8 are solids at 20 °C and have been recovered in yields of 60-83%. The orthorhombic structure of 1,2-C6H4S7 has been investigated by single-crystal X-ray diffraction analysis. The molecules are found to be located at sites of Cs symmetry and the motif of the C2S7 heterocycle is +-+-+-+-, with the torsion angle of zero at the carbon-carbon bond. The three internuclear SS distances measure 205.0(1), 203.7(1), and 205.7(1) pm.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 90
    Electronic Resource
    Electronic Resource
    Reaction of the Tetrachalcogenides [ME4(dppe)] (M = Pd, E = S; M = Pt, E = S, Se) with Activated Alkynes to Form Dithiolenes and Diselenolenes (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 933-938 
    Details
    ISSN: 1434-1948
    Keywords: Palladium ; Platinum ; Dithiolenes ; Diselenolenes ; Sulfur ; Selenium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tetrachalcogenides [ME4(dppe)] (M = Pd, E = S; M = Pt, E = S, Se) react with the activated alkynes RO2CC≡CCO2R (R = Me, Et) to form the dithiolenes and diselenolenes [M{E2C2(CO2R)2}(dppe)]; the structures of the compounds with E = S, R = Et have been determined by X-ray crystallography; [PdS4(dppe)] also reacts with the carbene complex [W(CO)5{C(OEt)C≡CPh}] to yield the bimetallic dithiolene [Pd{S2C2[C(OEt)W(CO)5]Ph}(dppe)].
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 91
    Electronic Resource
    Electronic Resource
    New Di- and Trinuclear Complexes with Pyrazolato Bridges. Crystal Structures of [{(C6F5)2Pd(μ-pz)(μ-Cl)}2Pd]2- and [(C6F5)2Pd(μ-pz)2Pd(η3-C4H7)] (pz = pyrazolate) (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 943-949 
    Details
    ISSN: 1434-1948
    Keywords: Pyrazolate complexes ; Palladium ; Platinum ; N ligands ; Bridging ligands ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Trinuclear complexes containing pyrazolate bridging ligands of the type [NBu4]2[{(C6F5)2 M(μ-pz)(μ-X)}2M′] (M, M′= Pd or Pt; X = Cl, OH, or pz) (Hpz = pyrazole) have been prepared using [NBu4][M(C6F5)2(acac)] (acac = acetylacetonate) or [NBu4]2[M2(C6F5)4(μ-OH)2] and [M′Cl2(Hpz)2] or [M′(Hpz)4]2+ as starting materials. Asymmetric homo- and heterobimetallic complexes of the types [NBu4][R2M(μ-pz)2Pd(η3-allyl)] and [R2M(μ-pz)2M′L2] (allyl = C3H5 or C4H7; L2 = 2 PEt3 or bipy; R = C6F5 or C6Cl5; M, M′ = Pd or Pt) have been obtained starting from [NBu4][MR2(pzHpz)] and [Pd(η3-allyl)(acac)] or [M′L2Cl2], respectively. The identity of the new complexes has been established by NMR (1H, 19F and 31P) spectroscopy. The crystal structure of [{(C6F5)2Pd(μ-pz)(μ-Cl)}2Pd]2- has an inversion centre, with a bent appearance of the Pd3(μ-pz)2(μ-Cl)2 moiety. The crystal structure of [(C6F5)2Pd(μ-pz)2Pd(η3-C4H7)] has also been determined by single-crystal X-ray diffraction, where a boat conformation of the central “Pd2N4” six-membered rings is observed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 92
    Electronic Resource
    Electronic Resource
    Rational Design of Homo and Hetero Hexanuclear Coordination Compounds: Syntheses and Magnetic Properties of [Cu2IIM4II] (M = Cu, Ni) Species and the Crystal Structure of {[Cu(tmen)(H2O)]2[Cu(tmen)]2[Cu2L](H2O)}(ClO4)4 · 2 H2O (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 951-957 
    Details
    ISSN: 1434-1948
    Keywords: Copper ; Nickel ; Amides ; Polynuclear complexes ; Magnetic properties ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New homo- and heterometallic hexanuclear complexes of formula {[Cu(tmen)(H2O)]2[Cu(tmen)]2[Cu2L](H2O)}(ClO4)4 ·2 H2O [Cu6-tmen] {[Cu(pmdien)]4[Cu2L]}(ClO4)4 · 4 H2O [Cu6-pmdien] and {[Ni(cyclam)]4[Cu2L]}(ClO4)4 · 4 H2O [Cu2Ni4-cyclam] [H8L = tetrakis(aminomethylene)methanetetrakis(oxamic acid), tmen = N,N,N′,N′-tetramethylethylenediamine, pmdien = N,N,N′,N′,N″-pentamethyldiethylenetriamine, and cyclam = 1,4,8,11-tetraazacyclotetradecane] have been synthesized. The crystal structure of [Cu6-tmen] has been determined by single-crystal X-ray diffraction. The structure consists of cationic {[Cu(tmen)(H2O)]2[Cu(tmen)]2[Cu2L](H2O)}4+ hexanuclear units. The hexanuclear cation is made up of two symmetry-related oxamato-bridged trinuclear units connected through the central carbon atom C(6) of the L8- ligand. Variable-temperature magnetic susceptibility measurements (1.8-300 K) have been performed for these series of complexes including the dinuclear precursors of formula Na4[Cu2L] · 10.5 H2O [Cu2-Na], (NMe4)4[Cu2L] · 4 H2O [Cu2-NMe4] and (PPh4)4[Cu2L] · 6 H2O [Cu2-PPh4]. The magnetic data have been interpreted. Evidence of a weak intramolecular ferromagnetic interaction between the two CuII ions in [Cu2L]4- has been observed. For the hexanuclear species, the interaction through the oxamato bridge was found to be equal to -6790, -2650, and -1643 yJ (-342, -133, and -82 cm-1) for [Cu6-tmen], [Cu6-pmdien], and [Cu2Ni4-cyclam], respectively. In these complexes, the weak intramolecular ferromagnetic coupling between the two CuII ions within the dinuclear synthon was masked by intermolecular interactions or local anisotropy.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 93
    Electronic Resource
    Electronic Resource
    Enantiomerically Pure Complexes of Manganese, Iron, and Zirconium with Pinene-Fused Boratabenzene Ligands - Structures ofexo-FeCp*(C13H17BNMe2) and exo,exo-ZrCl2(C13H17BNMe2)2 (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 979-986 
    Details
    ISSN: 1434-1948
    Keywords: Boron ; Transition metals ; Sandwich complexes ; Boratabenzene ; Pinene ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complexes of pinene-fused boratabenzene ligands [(1R,9R)6,10,10-trimethyl-4-boratatricyclo[7.1.1.02,7]undeca-2,4,6trienes] C13H17BX (with a: X = NMe2; b: X = OMe; c: X = Me) are described. The lithium salt Li(C13H17BNMe2) [Li(1a)] reacts with [Cp*Fe(NCMe)3]PF6 and with Mn(CO)3Br(py)2 to give diastereomeric mixtures FeCp*(C13H17BNMe2) (4a) and Mn(CO)3(C13H17BNMe2) (7). The mixture 4a undergoes solvolysis in methanol to produce methoxy compounds 4b, which in turn react with LiMe in Et2O to give methyl derivatives 4c. The lithium salts Li(C13H17BX) [Li(1a-c)] react with ZrCl4 in toluene or Et2O to give exo,exo-ZrCl2(C13H17BX)2 complexes (8a-c). The dimethyl derivative exo,exo-ZrMe2(C13H17BNMe2)2 (9) can also be prepared from 8a/LiMe in Et2O. NOE difference spectra have been analyzed to determine the configurations of the diastereomers and to establish a chemical shift criterion for assessing the configuration of the metal-ligand coordination. An independent confirmation of the product stereochemistries has been obtained by single-crystal X-ray structure determinations of exo-4a and 8a.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 94
    Electronic Resource
    Electronic Resource
    Protonation of [tpmRu(PPh3)2H]BF4 [tpm = Tris(pyrazolyl)methane] - Formation of Unusual Hydrogen-Bonded Species (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 993-1000 
    Details
    ISSN: 1434-1948
    Keywords: Ruthenium ; Dihydrogen complexes ; Dihydrogen bonding ; Hydride protonation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: in CD2Cl2 yielded, in a straightforward manner, the dicationic η2-dihydrogen complex [tpmRu(PPh3)2(H2)](BF4)2, which, as expected, is more acidic than its monocationic Tp [Tp = hydrotris(pyrazolyl)borate] analog [TpRu(PPh3)2(H2)]BF4 (pKa: 2.8 vs. 7.6). The complex [tpmRu(PPh3)2(H2)](BF4)2 is unstable towards H2 loss at ambient temperature. However, acidification of [tpmRu(PPh3)2H]BF4 with excess aqueous HBF4 or aqueous triflic acid in [D8]THF gave very interesting results. Variable-temperature 1H- and 31P-NMR studies revealed that the aqueous acid did not fully protonate the metal hydride to form the dihydrogen complex, but a hydrogen-bonded species was obtained. The feature of this species is that the strength of its Ru-H···H-(H2O)m interaction decreases with temperature; this phenomenon is unusual because other complexes containing dihydrogen bonds show enhanced M-H···H-X interaction as the temperature is lowered. Decrease of the dihydrogen-bond strength with temperature in the present case can be attributed to the decline of acidity that results from the formation of larger H+(H2O)n (n 〉 m) clusters at lower temperatures; steric hindrance of these large clusters also contribute to the weakening of the dihydrogen bonding interactions. At higher temperatures, facile H/H exchange occurs in Ru-H···H-(H2O)m via the intermediacy of a “hydrogen-bonded dihydrogen complex” Ru-(H2)···(H2O)m. To investigate the effect of the H+(H2O)m cluster size on the strength of the dihydrogen bonding in [tpmRu(PPh3)2H]+, molecular orbital calculations at the B3LYP level have been performed on model systems, [tpmRu(PH3)2H]+ + H+(H2O) and [tpmRu(PH3)2H]+ + H+(H2O)2. The results provide further support to the notion that the formation of larger H+(H2O)n clusters weakens the Ru-H····H(H2O)n dihydrogen bonding interaction.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 95
    Electronic Resource
    Electronic Resource
    Spectroscopic Study of the Hydration Equilibria and Water Exchange Dynamics of Lanthanide(III) Complexes of 1,7-Bis(carboxymethyl)-1,4,7,10-tetraazacyclododecane (DO2A) (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 1001-1006 
    Details
    ISSN: 1434-1948
    Keywords: Imaging agents ; Lanthanides ; NMR spectroscopy ; DNA cleavage ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hydration state of a series of [Ln(DO2A)(H2O)n]+ complexes in aqueous solution at pH = 6.4-7.0 was studied by measuring the lanthanide-induced 17O shifts (LIS) of water [Ln includes elements from Ce to Yb; DO2A = 1,7-bis(carboxymethyl)-1,4,7,10-tetraazacyclododecane]. Their contact contribution, obtained from Reilley plots, indicated a decrease in the inner-sphere water coordination number of the [Ln(DO2A)(H2O)n]+ complexes from n = 3 (Ce-Eu), to n = 2 (Tb-Yb). A temperature-dependent UV/Vis absorption study of the 578-582 nm 7F0 → 5D0 transition band of [Eu(DO2A)(H2O)n]+ in aqueous solution showed that this complex is present in an equilibrium between eight- and nine-coordinate species with n = 2 and n = 3, respectively. The hydration equilibrium parameters (2 ↔ 3), K2-3298 = 4.0 ± 0.2, ΔH2-30 = -12.1 ± 1 kJ mol-1 and ΔS2-30 = -28.9 ± 3 J mol-1 K-1,correspond to an average hydration number of 2.65-2.85 in the temperature range 273-363 K. A variable temperature, multiple field 17O NMR study combined with direct EPR measurements of the transverse electronic relaxation rates has been used to obtain the parameters characterizing water exchange, rotation and electronic relaxation, all influencing the proton relaxivity of [Gd(DO2A)(H2O)2-3]+. The small increase in the water exchange rate of [Gd(DO2A)(H2O)2-3]+ (kex298 = (10 ± 5) × 106s-1) relative to that of[Gd(DOTA)(H2O)]- (4.8 × 106 s-1) is a consequence of an unfavorable interplay of charge and hydration equilibria. The value of τR298 = 40 ± 1 ps is short, and the electronic relaxation rate (1/T2e ≍ 1.2 × 1010 s-1) is fast relative to [Gd(DOTA)(H2O)]- (1.3-2.4 × 109 s-1 for B = 0.34 T). These parameters negate to some extent the expected increase in proton relaxivity of the [Gd(DO2A)(H2O)2-3]+ complex.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99338_s.pdf or from the author.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 96
    Electronic Resource
    Electronic Resource
    Benzimidazole, Benzothiazole and Benzoxazole Ruthenium(II) Complexes; Catalytic Synthesis of 2,3-Dimethylfuran (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 29-32 
    Details
    ISSN: 1434-1948
    Keywords: Arene complexes ; Ruthenium ; Benzimidazole ; Benzothiazole ; Benzoxazole ; Cycloisomerisation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fourteen ruthenium(II) complexes of the type [RuCl2(η6-arene)L], (arene = 1,4-MeC6H4Pri or C6Me6; L = benzimidazole derivative in which the NH group is substituted by N-alkyl or isoelectronic O or S atoms) have been prepared by cleavage of [RuCl2(η6-arene)]2 with the N-heterocycle L. Their spectroscopic and electrochemical properties are described. The effect of the nature of the benzazole (L) on the catalytic activity of these complexes for the intramolecular cyclization of (Z)-3-methylpent-2-en-4-yn-1-ol into 2,3-dimethylfuran has also been studied; the benzimidazole complexes were found to be the most active.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 97
    Electronic Resource
    Electronic Resource
    Mononuclear Ni, Pd and Pt Complexes with ′S3′2- Thioether Thiolate and HNPnPr3 Phosphorane Imine Ligands [′S3′2- = Bis(2-mercaptophenyl)sulfide (2-)] (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 59-63 
    Details
    ISSN: 1434-1948
    Keywords: Phosphorane imine ; Sulfur ligands ; Nickel ; Palladium ; Platinum ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of the trinuclear [M(′S3′)]3 complexes {M = Ni (4), Pd (5), Pt (6); ′S3′2- = bis(2-mercaptophenyl)sulfide (2-)} with HNPnPr3 yielded the new phosphorane imine complexes [M(NHPnPr3)(′S3′)] {M = Ni (1), Pd (2), Pt (3)}. The complexes 1-3 have been completely characterized and are rare examples of mononuclear phosphorane imine complexes with late transition metals. Spectroscopic and structural results indicate that the HNPnPr3 ligands favor the ylidic structure when binding to [M(′S3′)] fragments. X-ray structure determinations showed that [M(NHPnPr3)(′S3′)] complexes associate through N-H···S(thiolate) bridges to give centrosymmetric dimers.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 98
    Electronic Resource
    Electronic Resource
    Synthesis, Crystal Structures and Lithium Encapsulation by Some Phenolic Aza Cages (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 51-57 
    Details
    ISSN: 1434-1948
    Keywords: Cages ; Synthesis ; Lithium ; Crystal structures ; Chromophores ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three new macrocyclic cages 1, 2 and 3, able to selectively encapsulate the lithium ion, were studied. The synthesis and characterization of 2 and 3 are reported. The basicity behaviour of the three cages was investigated by spectrophotometry and by 1H and 13C NMR spectroscopy. The protonation constants were determined by potentiometric methods in aqueous solution (I = 0.15 mol dm-3 NMe4Cl, T = 298 ± 0.1 K) and were found to be logK1 = 11.67(5), 10.77(7), 11.17(7); logK2 = 7.76(5), 5.7(1), 5.6(1); logK3 = 1.3(1), 2.4(1), 1.9(1) for 1, 2, and 3, respectively. The lithium equilibrium complex formation Li+ + L = LiLH-1 + H+ was monitored by 13C and 7Li NMR spectroscopy, as well as by spectrophotometric and potentiometric techniques; log values of -9.1(1) and -8.0(1) were found for 1 and 3, respectively. For 2, precipitation of the lithium complex occurs. UV/Vis studies in aqueous solution show a significant shift towards high energy of the λmax in the lithium complex, indicating the potential for application of these ligands in colourimetric analysis. The crystal structure of 1 was examined by single crystal X-ray diffraction. Data collection was performed on two samples, namely 1a and 1b, obtained from two different crystallization procedures. Crystals of 1a are monoclinic, space group P21/n, while 1b crystallized in an orthorhombic space group Pc21b. The cell parameters are a = 12.423(3), b = 14.378(9), c = 28.436(7) Å, β = 93.74(2)° for 1a, and a = 10.674(4), b = 14.408(2), c= 17.034(2) Å for 1b. Molecular simulations were carried out on both conformational isomers 1a and 1b, with results indicating that the two isomers have essentially the same flexibility.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 99
    Electronic Resource
    Electronic Resource
    Solution Equilibria in YbDOTMA, a Chiral Analogue of One of the Most Successful Contrast Agents for MRI, GdDOTA (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 75-82 
    Details
    ISSN: 1434-1948
    Keywords: Macrocyclic ligands ; Conformational equilibria ; EXSY spectroscopy ; Lanthanide-induced shifts ; Solution structure ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure and the conformational equilibria in aqueous and methanolic solutions of YbDOTMA (DOTMA = (1R,4R,7R,10R)-α,α′,α′′,α′′′′-tetramethyl-1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) are investigated and the dynamics studied by means of NMR methods. The presence of two isomeric forms in slow exchange is confirmed and quantitatively characterized by EXSY. The exchange peaks are assigned to the inversion of the conformation of the macrocycle ring. No evidence is obtained of a reorientation of the methyl acetate substituents. The protons switch between positions with the same geometrical factors, i.e. positions that would have the same pseudocontact shifts were it not for the different magnetic susceptibility anisotropies of the two species; steady-state NOE spectra on the major form allow unequivocal assignment of the conformations of the two isomers.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99141_s.pdf or from the author.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
  • 100
    Electronic Resource
    Electronic Resource
    Coordination of CO, NO, N2H2, and Other Nitrogenase Relevant Small Molecules to Sulfur-Rich Ruthenium Complexes with the New Ligand ‘tpS4’2- = 1,2-Bis(2-mercaptophenylthio)phenylene(2-) (2000)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 1079-1089 
    Details
    ISSN: 1434-1948
    Keywords: Ruthenium ; S ligands ; Hydrazine ; Diazene ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the search for ruthenium complexes with sulfur-dominated coordination spheres that bind, activate, or stabilize nitrogenase relevant molecules, complexes containing the new and robust tetradentate ligand ‘tpS4’-H2 were synthesized. Treatment of [RuCl2(PPh3)3] with ‘tpS4’2- gives [Ru(PPh3)2(‘tpS4’)] (1), which contains two labile PPh3 ligands. The reaction of 1 with PEt3 or DMSO led to substitution of both PPh3 ligands, yielding [Ru(PEt3)2(‘tpS4’)] (2) and [Ru(DMSO)2(‘tpS4’)] (3), respectively. When treated with nitrogenous ligands, complex 1 lost only one PPh3 ligand to yield [Ru(L)(PPh3)(‘tpS4’)] complexes where L = py (7), NH3 (8), N2H4 (9), NH2NHMe (10), and CH3CN (12), all of which are labile. The labile acetonitrile complex [Ru(CH3CN)(PPh3)(‘tpS4’)] (12) proved to be particularly suited as a precursor for the syntheses of other [Ru(L)(PPh3)(‘tpS4’)] complexes. The 18 and 19 valence electron NO complexes [Ru(NO)(PPh3)(‘tpS4’)]BF4 (13) and [Ru(NO)(PPh3)(‘tpS4’)] (14), (NEt4)[Ru(N3)(PPh3)(‘tpS4’)] (15), [Ru(I)(PPh3)(‘tpS4’)] (16), and [Ru(N3)(PPh3)(‘tpS4’)] (17) were obtained starting from complex 12. The labile mononuclear hydrazine complex [Ru(N2H4)(PPh3)(‘tpS4’)] (9) gave the dinuclear complex [μ-N2H4{Ru(PPh3)(‘tpS4’)}2] (18) by dissociation of hydrazine. The dinuclear diazene complex [μ-N2H2{Ru(PPh3)(‘tpS4’)}2] (19) was obtained by oxidation of 9 and more readily from [Ru(CH3CN)(PPh3)(‘tpS4’)] (12) and N2H2, which was generated in situ from K2N2(CO2)2 and acetic acid. The molecular structures of 7, 13, 16, 18, and 19 were determined by X-ray structure analyses. The complexes 18 and 19 represent the first complexes containing the hydrazine/diazene couple, which enables us to compare both the bonding features and the formation of N-H···S bridges when hydrazine and diazene bind to transition metal sulfur sites.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Location Call Number Expected Availability
    BibTip Others were also interested in ...
    Paper (German National Licenses)
Close ⊗
This website uses cookies and the analysis tool Matomo. More information can be found here...