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  • Wiley-Blackwell  (471,615)
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  • 101
    Publication Date: 2017-04-04
    Description: The present-day sea level variations and geodetically observed ground deformations in the Mediterranean area are normally ascribed to the combined effect of tectonic or human-driven subsidence and postglacial uplift as a result of the melting of the major Pleistocene ice sheets. However, another potential cause of deformation, only marginally considered to date, is the melting of the glacier that covered the Alps during the last glacial maximum (LGM). The aim of this paper is to predict the long-term sea level variations induced by the melting of both the late-Pleistocene and Alpine ice sheets and compare our results with the relative sea level (RSL) observations available in the Mediterranean region. This task is accomplished solving the sea level equation (SLE) for a spherically symmetric viscoelastic Earth. Our analysis shows that the melting of the Alpine glacier has marginally affected the Holocene sea level variations in the near-field sites in southern France (Marseilles and Roussillon) and the central Tyrrhenian sea (Civitavecchia), and that the RSL predictions are significantly sensitive to the chronology of the remote ice aggregates. The computations, which are performed using a specific mantle viscosity profile consistent with global observations of RSL rise, show that the uplift rate driven by the Alpine isostatic readjustment may account for up to 1/3 of the rates observed at GPS stations in the western portion of the chain. Our results suggest that a thorough modelization of both near- and far-field ice sheets is necessary to gain a better insight into the present-day deformations and sea level variations in the Mediterranean region.
    Description: Published
    Description: 137-147
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: JCR Journal
    Description: restricted
    Keywords: Alpine glacier ; glacial rebound ; mantle viscosity ; sea level variations ; 04. Solid Earth::04.07. Tectonophysics::04.07.02. Geodynamics
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 102
    Publication Date: 2017-04-04
    Description: Although characterized by low seismicity, the Monferrato area of north-western Italy was affected by earthquakes, of magnitude M5.1 and M4.8, in 2000 and 2001. At the same time, marked changes were recorded in water temperature and chemistry in several wells within the epicentral area. In May 2004, an automatic network for the continuous monitoring of groundwater was installed in selected wells to study the phenomenon. Here, we report on data collected during a 3-year period of groundwater monitoring. During the first year, episodes of water heating (by up to 20°C) were observed in one monitored well. The temporal analysis of the seismic activity recorded in the area revealed as almost all seismic events occurred during the period of elevated water temperatures. The similar timing of earthquakes and groundwater-temperature anomalies suggests that both may be triggered by the same processes acting in the crust.
    Description: Published
    Description: 142-149
    Description: JCR Journal
    Description: reserved
    Keywords: groundwater monitoring ; pore fluid pressure; ; tectonic stress ; 03. Hydrosphere::03.02. Hydrology::03.02.02. Hydrological processes: interaction, transport, dynamics ; 03. Hydrosphere::03.02. Hydrology::03.02.04. Measurements and monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 103
    Publication Date: 2020-02-24
    Description: Integration of geologic, geomorphologic and seismologic data sets is used to reconstruct the recent tectonic evolution and active deformation pattern in the Val d’Agri area, located in the seismically active axial sector of the Southern Apennines (Italy). The western portion of the Apennines thrust belt has been affected by Pliocene–Quaternary extension during easterly roll-back and crustal delamination of the Adriatic slab. The bulk of Quaternary extension has been accommodated bySW-dipping oblique and normal faults,which have attained mature morphologic and structural features and, nowadays, separate mountain ranges from intermontane basins. However, in the present seismogenic belt, coseismic faulting locally occurs on NE-dipping structures, which might cut the inherited Pleistocene landscape. In theVal d’Agri basin, in spite of the large Early–Middle Pleistocene, displacement occurred on SW-dipping faults bordering its eastern flank, our investigations show that the recent basin evolution has been controlled by a NE-dipping fault system (Monti della Maddalena fault system, MMFS). This fault system cuts across the Monti della Maddalena range, west of the Agri valley and has not yet created an evident tectonic landscape. Notwithstanding, fault motion since the Middle Pleistocene might explain geomorphologic and hydrographic anomalies of the Agri river and its valley, where fault-controlled subsidence has captured the river course and produced an aggrading plain within a regional uplift context. Recent and ongoing motion is documented by fault scarplets in loose deposits, 14C ages of palaeosols and the spatial relation with low to moderate instrumental seismicity. Results from fault kinematic analysis are compatible with fault-plane solutions of local and regional seismic events, and indicate ∼NE–SW oriented extension. Recognition of the MMFS as a potential seismogenic fault increases the longitudinal extent of the NE-dipping, morphologically immature seismic sources in the Southern Apennines and argues against the range-bounding fault model for active extension in the region. The regional size of the NE-dipping seismogenic belt may result from impingement of a mantle wedge beneath the Apenninic chain and possibly track the external front of crustal delamination.
    Description: Published
    Description: 591-609
    Description: 3.2. Tettonica attiva
    Description: JCR Journal
    Description: reserved
    Keywords: active tectonics ; crustal deformation ; earthquakes ; geomorphology ; normal faulting ; Southern Italy ; 04. Solid Earth::04.04. Geology::04.04.01. Earthquake geology and paleoseismology ; 04. Solid Earth::04.04. Geology::04.04.03. Geomorphology ; 04. Solid Earth::04.04. Geology::04.04.09. Structural geology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 104
    Publication Date: 2020-02-24
    Description: After an earthquake, rapid, real-time assessment of hazards such as ground shaking and tsunami potential is important for early warning and emergency response. Tsunami potential depends on seafloor displacement, which is related to the length, L, width, W, mean slip, D, and depth, z, of earthquake rupture. Currently, the primary discriminant for tsunami potential is the centroid-moment tensor magnitude, MCMT, representing the seismic potency LWD, and w estimated through an indirect, inversion procedure. The obtained MCMT and the implied LWD w value vary with the depth of faulting, assumed earth model and other factors, and is only available 30 min or more after an earthquake. The use of more direct procedures for hazard assessment, when available, could avoid these problems and aid in effective early warning. Here we present a direct procedure for rapid assessment of earthquake tsunami potential using two, simple measures on P-wave seismograms—the dominant period on the velocity records, Td, and the likelihood that the high-frequency, apparent rupture-duration, T0, exceeds 50–55 s. T0 can be related to the critical parameters L and z, while Td may be related to W, D or z. For a set of recent, large earthquakes, we show that the period-duration product T T gives more information on tsunami impact and size than MCMT and other currently used d0w discriminants. All discriminants have difficulty in assessing the tsunami potential for oceanic strike-slip and backarc or upper plate, intraplate earthquake types. Our analysis and results suggest that tsunami potential is not directly related to the potency LWD from the ‘seismic’ faulting model, as is assumed with the use of the MCMT discriminant. Instead, knowledge of w rupture length, L, and depth, z, alone can constrain well the tsunami potential of an earthquake, with explicit determination of fault width, W, and slip, D, being of secondary importance. With available real-time seismogram data, rapid calculation of the direct, period-duration discriminant can be completed within 6–10 min after an earthquake occurs and thus can aid in effective and reliable tsunami early warning.
    Description: Published
    Description: 283-291
    Description: JCR Journal
    Description: restricted
    Keywords: earthquake dynamics ; earthquake source observation ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 105
    Publication Date: 2020-02-24
    Description: This article analyzes the ocean forecast response to surface vector wind (SVW) distributions generated by a Bayesian hierarchical model (BHM) developed in Part I of this series. A new method for ocean ensemble forecasting (OEF), the socalled BHM-SVW-OEF, is described. BHM-SVW realizations are used to produce and force perturbations in the ocean state during 14 day analysis and 10 day forecast cycles of the Mediterranean Forecast System (MFS). The BHM-SVW-OEF ocean response spread is amplified at the mesoscales and in the pycnocline of the eddy field. The new method is compared with an ensemble response forced by European Centre for Medium-Range Weather Forecasts (ECMWF) ensemble prediction system (EEPS) surface winds, and with an ensemble forecast started from perturbed initial conditions derived froman ad hoc thermocline intensified random perturbation (TIRP) method. The EEPS-OEF shows spread on basin scales while the TIRP-OEF response is mesoscale-intensified as in the BHM-SVW-OEF response. TIRP-OEF perturbations fill more of the MFS domain, while the BHM-SVW-OEF perturbations are more location-specific, concentrating ensemble spread at the sites where the ocean-model response to uncertainty in the surface wind forcing is largest.
    Description: Published
    Description: 879–893
    Description: JCR Journal
    Description: embargoed_20140501
    Keywords: forecast uncertainty ; 03. Hydrosphere::03.01. General::03.01.03. Global climate models
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 106
    Publication Date: 2020-03-16
    Description: Post-seismic relaxation is known to occur after large or moderate earthquakes, on time scales ranging from days to years or even decades. In general, long-term deformation following seismic events has been detected by means of standard geodetic measurements, although seismic instruments are only used to estimate short timescale transient processes. Albeit inertial seismic sensors are also sensitive to rotation around their sensitive axes, the recording of very slow inclination of the ground surface at their standard output channels is practically impossible, because of their design characteristics. However, modern force-balance, broad- band seismometers provide the possibility to detect and measure slow surface inclination, through the analysis of the mass position signal. This output channel represents the integral of the broad-band velocity and is generally considered only for state-of-health diagnostics. In fact, the analysis of mass position data recorded at the time of the 2009 April 6, L’Aquila (MW = 6.3) earthquake, by a closely located STS-2 seismometer, evidenced the occurrence of a very low frequency signal, starting right at the time of the seismic event. This waveform is only visible on the horizontal components and is not related to the usual drift coupled with the temperature changes. This analysis suggests that the observed signal is to be ascribed to slowly developing ground inclination at the station site, caused by post-seismic relaxation following the main shock. The observed tilt reached 1.7 × 10−5 rad in about 2 months. This estimate is in very good agreement with the geodetic observations, giving comparable tilt magnitude and direction at the same site. This study represents the first seismic analysis ever for the mass position signal, suggesting useful applications for usually neglected data.
    Description: Published
    Description: 1717-1724
    Description: 3.1. Fisica dei terremoti
    Description: JCR Journal
    Description: restricted
    Keywords: Seismic cycle ; Earthquake source observations ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 107
    Publication Date: 2017-04-03
    Description: On 2009 April 6 a Mw = 6.3 earthquake struck the Abruzzi region (Central Italy) and caused severe destruction in L’Aquila and the surrounding area. In this work we present a Finite Element analysis of the event based on a realistic complex 3-D model, accounting for topographic relief and rheological heterogeneities deduced from local tomography. Finite Element computed Green’s functions were implemented in a linear inversion of GPS coseismic displacements, to retrieve the slip distribution on the rupture plane. The inverted slip models basically agree with previous studies carried out on homogeneous domains, but reveal the presence of a single high slip patch, whereas half-space or 1-D approaches obtain a more complex slip pattern. Our results point out that the introduction of 3-D features significantly influences the obtained source model, suggesting a trade-off between domain complexities and source details.
    Description: Published
    Description: 1339–1358
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: JCR Journal
    Description: restricted
    Keywords: Numerical approximations and analysis ; Seismicity and tectonics ; Dynamics and mechanics of faulting ; L'Aquila earthquake ; 04. Solid Earth::04.07. Tectonophysics::04.07.02. Geodynamics
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 108
    Publication Date: 2017-04-04
    Description: The accurate determination of locations and magnitudes of seismic events in a monitored region is important for many scientific, industrial and military studies and applications; for these purposes a wide variety of seismic networks are deployed throughout the world. It is crucial to know the performance of these networks not only in detecting and locating seismic events of different sizes throughout a specified source region, but also by evaluating their location errors as a function of the magnitude and source location. In this framework, we have developed a method for evaluating network performance in surface and borehole seismic monitoring. For a specified network geometry, station characteristics and a target monitoring volume, the method determines the lowest magnitude of events that the seismic network is able to detect (Mw detect), and locate (Mw loc) and estimates the expected location and origin time errors for a specified magnitude. Many of the features related to the seismic signal recorded at a single station are considered in this methodology, including characteristics of the seismic source, the instrument response, the ambient noise level, wave propagation in a layered, anelastic medium and uncertainties on waveform measures and the velocity model. We applied this method to two different network typologies: a local earthquake monitoring network, Irpinia Seismic Network (ISNet), installed along the Campania-Lucania Apennine chain in Southern Italy, and a hypothetic borehole network for monitoring microfractures induced during the hydrocarbon extraction process in an oil field. The method we present may be used to aid in enhancing existing networks and/or understanding their capabilities, such as for the ISNet case study, or to optimally design the network geometry in specific target regions, as for the borehole network example.
    Description: Published
    Description: 793-806
    Description: 4.1. Metodologie sismologiche per l'ingegneria sismica
    Description: JCR Journal
    Description: restricted
    Keywords: Earthquake ground motions ; Computational seismology ; 04. Solid Earth::04.06. Seismology::04.06.10. Instruments and techniques
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  • 109
    Publication Date: 2017-04-03
    Description: Computing the magnitude of an earthquake requires correcting for the propagation effects from the source to the receivers. This is often accomplished by performing numerical simulations using a suitable Earth model. In this work, the energy magnitude Me is considered and its determination is performed using theoretical spectral amplitude decay functions over teleseismic distances based on the global Earth model AK135Q. Since the high frequency part (above the corner frequency) of the source spectrum has to be considered in computing Me, the influence of propagation and site effects may not be negligible and they could bias the single station Me estimations. Therefore, in this study we assess the inter- and intrastation distributions of errors by considering the Me residuals computed for a large data set of earthquakes recorded at teleseismic distances by seismic stations deployed worldwide. To separate the inter- and intrastation contribution of errors, we apply a maximum likelihood approach to the Me residuals. We show that the interstation errors (describing a sort of site effect for a station) are within ±0.2 magnitude units for most stations and their spatial distribution reflects the expected lateral variation affecting the velocity and attenuation of the Earth's structure in the uppermost layers, not accounted for by the 1-D AK135Q model. The variance of the intrastation error distribution (describing the record-to-record component of variability) is larger than the interstation one (0.240 against 0.159), and the spatial distribution of the errors is not random but shows specific patterns depending on the source-to-station paths. The set of coefficients empirically determined may be used in the future to account for the heterogeneities of the real Earth not considered in the theoretical calculations of the spectral amplitude decay functions used to correct the recorded data for propagation effects.
    Description: Published
    Description: 1444-1454
    Description: JCR Journal
    Description: restricted
    Keywords: time series analysis ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 110
    Publication Date: 2017-04-04
    Description: The monitoring of crustal motions in Northern Victoria Land (NVL) of Antarctica by means of episodic GPS stations (EGPSs) provides an accurate and dense (∼50-km spaced) velocity field. The data, gathered starting in Austral summer 1999, derive from a series of benchmarks belonging to the Victoria Land Network for DEFormation control (VLNDEF) geodetic network. The velocity uncertainties are checked on the basis of length and returning time of the episodic surveys, to obtain a meaningful strain rate field by means of a least-square computation where the contribution of a GPS station is weighted by the inverse square of its velocity error. The study shows that the NVL is characterized by a complex kinematics and that, although three subregions with different prevailing deformational behaviour can be recognized, the single blocks cannot be resolved because too few stations exist. Only features having 150–200 km size at least can be recognized. Moreover, it is demonstrated that an appropriate data processing of EGPS data can lead to an accurate evaluation of the strain rate field even in a harsh environment like Antarctica.
    Description: Published
    Description: 851-862
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: JCR Journal
    Description: reserved
    Keywords: Time-series analysis ; Satellite geodesy ; Geomorphology ; Antarctica ; 04. Solid Earth::04.07. Tectonophysics::04.07.02. Geodynamics
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 111
    Publication Date: 2017-04-04
    Description: The Gulf of Manfredonia and the Tavoliere Plain have experienced intense human colonization since the neolithic times. There is past evidence in the study area of a Roman-age settlement historically known as Salapia, probably located close to the salt-production ponds. In particular, several portions of a partly submerged ancient pier-like structure were found close to Torre Pietra town. This structure has been interpreted as a portion of a dragged-ship channel that connected the town of Salapia to the sea. In this article we discuss the results of a high-resolution geophysical prospecting of the Margherita di Savoia offshore archaeological site (Puglia, Italy). We collected magnetic gradiometric and bathymetric data to map the submerged remains of Salapia harbour. We found evidence of an offshore projection of a Torre Pietra pier-like structure, identifying the direction of the ship channel and possibly the location of the harbour’s defensive post
    Description: Published
    Description: 89-101
    Description: 3.4. Geomagnetismo
    Description: JCR Journal
    Description: restricted
    Keywords: Marine magnetic survey; ; Manfredonia Gulf ; Roman archaeological finds ; buried ruins ; analytic signal; ; horizontal gradient ; 04. Solid Earth::04.05. Geomagnetism::04.05.04. Magnetic anomalies ; 05. General::05.01. Computational geophysics::05.01.01. Data processing
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 112
    Publication Date: 2017-04-04
    Description: The overall picture of Mount Etna deformation emerging since a couple of decades of geodetic surveys shows effects of magma accumulation, characterized by inflation/deflation cycle, accompanied by a sliding instability of the southeast flank, whose manifestation is an increase in the horizontal deformation away from the volcano summit. This is a very interesting case to test whether advanced models, taking into account topography, internal structure and frictional rheology, may contribute to a better understanding of the complex interplay among mechanical response, magmatic activity and gravitational load occurring in a volcanic system. Using finite element numerical models we make predictions of surface displacements associated with a simple expansion source and with a dike like vertical discontinuity. A new methodology is developed to initalize the lithostatic stress field according to the material and geometrical complexities of the models considered. Our results show that, while an amplification of the horizontal displacement can be easily obtained up to a maximum distance of 10 km from the source, we have not been able to find any onfiguration to extend further this signal. For the case of Mount Etna this suggests that the large horizontal displacements observed in the east flank along the coast cannot be directly related to magma accumulation below the volcano's summit.
    Description: Published
    Description: 939-953
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: JCR Journal
    Description: partially_open
    Keywords: Numerical solutions ; Space geodetic surveys ; Elasticity and anelasticity ; Eruption mechanisms and flow emplacement ; Volcanic hazards and risks ; 04. Solid Earth::04.01. Earth Interior::04.01.02. Geological and geophysical evidences of deep processes
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 113
    Publication Date: 2017-04-04
    Description: The Solfatara is one of the major volcanoes of the Phlegrean Fields (Campi Flegrei) volcanic complex, and it is located in a densely populated area a few kilometres west of the city of Naples. It is an active resurgent caldera that has been characterized by a rich history of surface–ground deformation and soil diffuse degassing and fumarolic emissions, which are indications of the top of a hydrothermal plume. A seismic survey was completed in May 2009 for the characterization of the main subsurface features of the Solfatara. Using the complete data set, we have carried out surface wave inversion with high spatial resolution. A classical minimization of a least-squares objective function was first computed to retrieve the dispersion curves of the surface waves. Then, the fitting procedure between the data and a three-sedimentlayer forward model was carried out (to a depth of 7 m), using an improved version of the neighbourhood algorithm. The inversion results indicate a NE-SW fault, which is not visible at the surface. This was confirmed by a temperature survey conducted in 2010. A passive seismic experiment localized the ambient noise sources that correlate well with the areas of high CO2 flux and high soil temperatures. Finally, considering that the intrinsic attenuation is proportional to the frequency, a centroid analysis provides an overview of the attenuation of the seismic waves, which is closely linked to the petrophysical properties of the rock. These different approaches that merge complete active and passive seismic data with soil temperature and CO2 flux maps confirm the presence of the hydrothermal system plume. Some properties of the top of the plume are indicated and localized.
    Description: Published
    Description: 1725–1733
    Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive
    Description: 2.4. TTC - Laboratori di geochimica dei fluidi
    Description: 4.5. Studi sul degassamento naturale e sui gas petroliferi
    Description: JCR Journal
    Description: restricted
    Keywords: Inverse theory ; Tomography ; Hydrothermal systems ; Europe ; 03. Hydrosphere::03.02. Hydrology::03.02.04. Measurements and monitoring ; 03. Hydrosphere::03.04. Chemical and biological::03.04.05. Gases ; 04. Solid Earth::04.04. Geology::04.04.11. Instruments and techniques ; 04. Solid Earth::04.04. Geology::04.04.12. Fluid Geochemistry
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  • 114
    Publication Date: 2017-04-04
    Description: The magnetic properties (first-order reversal curves, ferromagnetic resonance and decomposition of saturation remanent magnetization acquisition) of Magnetovibrio blakemorei, a cultivated marine magnetotactic bacterium, differ from those of other magnetotactic species from sediments deposited in lakes and marine habitats previously studied. This finding suggests that magnetite produced by some magnetotactic bacteria retains magnetic properties in relation to the crystallographic structure of the magnetic phase produced and thus might represent a ‘magnetic fingerprint’ for a specific magnetotactic bacterium. The use of this fingerprint is a non-destructive, new technology that might allow for the identification and presence of specific species or types of magnetotactic bacteria in certain environments such as sediments.
    Description: Published
    Description: 664-668
    Description: 1.8. Osservazioni di geofisica ambientale
    Description: 2.2. Laboratorio di paleomagnetismo
    Description: 3.8. Geofisica per l'ambiente
    Description: JCR Journal
    Description: restricted
    Keywords: batteri magnetotattici ; magnetite ; 03. Hydrosphere::03.01. General::03.01.06. Paleoceanography and paleoclimatology ; 04. Solid Earth::04.05. Geomagnetism::04.05.09. Environmental magnetism
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 115
    Publication Date: 2017-10-06
    Description: In this study we have determined detailed Vp and Vs seismic velocity models of the Ionian lithosphere subducting beneath the Tyrrhenian basin and of the surrounding mantle, by applying a post-processing technique to a large sample of local earthquake tomography studies. Our seismic velocity models permit us to infer the presence of low velocity anomalies within the slab, which we interpret as regions that are partially hydrated by fluids released during the subduction process. A petrological interpretation of the velocity anomalies gives new details on the magmatism of the volcanic Aeolian arc. Furthermore our velocity models provide a more detailed description of the boundary of the slab and its connection with the large seismically active Tindari-Letojanni strike slip system. Finally these results allow describing in detail some features of the slab as the presence of lateral and vertical tears. In conclusion, the obtained models provide some constraints for inferences on mantle circulation, and on the geodynamical evolution of the central-western Mediterranean.
    Description: Published
    Description: 751-764
    Description: 2.5. Laboratorio per lo sviluppo di sistemi di rilevamento sottomarini
    Description: JCR Journal
    Description: reserved
    Keywords: Tomography, petrology, Ionian slab ; 04. Solid Earth::04.06. Seismology::04.06.07. Tomography and anisotropy
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  • 116
    Publication Date: 2020-02-24
    Description: A Bayesian hierarchical model (BHM) is developed to estimate surface vector wind (SVW) fields and associated uncertainties over the Mediterranean Sea. The BHM–SVW incorporates data-stage inputs from analyses and forecasts of the European Centre for Medium-Range Weather Forecasts (ECMWF) and SVW retrievals from the QuikSCAT data record. The process-model stage of the BHM–SVW is based on a Rayleigh friction equation model for surface winds. Dynamical interpretations of posterior distributions of the BHM–SVW parameters are discussed. Ten realizations from the posterior distribution of the BHM–SVW are used to force the data-assimilation step of an experimental ensemble ocean forecast system for the Mediterranean Sea in order to create a set of ensemble initial conditions. The sequential data-assimilation method of the Mediterranean forecast system (MFS) is adapted to the ensemble implementation. Analyses of sample ensemble initial conditions for a single data-assimilation period in MFS are presented to demonstrate the multivariate impact of the BHM–SVW ensemble generation methodology. Ensemble initial-condition spread is quantified by computing standard deviations of ocean state variable fields over the ten ensemble members. The methodological findings in this article are of two kinds. From the perspective of statistical modelling, the process-model development is more closely related tophysicalbalances than inpreviousworkwithmodels for the SVW.Fromthe ocean forecast perspective, the generation of ocean ensemble initial conditions via BHM is shown to be practical for operational implementation in an ensemble ocean forecast system. Phenomenologically, ensemble spread generated via BHM–SVW occurs on ocean mesoscale time- and space-scales, in close association with strong synoptic-scale wind-forcing events. A companion article describes the impacts of the BHM–SVW ensemble method on the ocean forecast in comparisons with more traditional ensemble methods.
    Description: Published
    Description: 858–878
    Description: JCR Journal
    Description: embargoed_20140501
    Keywords: QuikSCAT surface winds ; 03. Hydrosphere::03.01. General::03.01.05. Operational oceanography
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  • 117
    Publication Date: 2020-02-24
    Description: In this study, new intensity prediction equations are derived for Central Asia, considering about 6000 intensity data points from 66 earthquakes encompassing the surface-wave magnitude range of 4.6–8.3. The suitability of the functional form used for constructing the model is assessed by comparing its predictions with those achieved through a non-parametric model. The parametric regressions are performed considering different measures of the source-to-site distance, namely the hypocentral, epicentral and the extended distance metrics. The latter is defined as the minimum distance from the site to a line crossing the epicentres, oriented along the strike of the earthquake and having a length estimated from the event’s magnitude. Although the extended distance is introduced as a preliminary attempt to improve the prediction capability of the model by considering the finiteness of the fault extension, the standard deviation of the residual distribution obtained considering the extended distance (σ = 0.734) does not show an improvement with respect to the results for the epicentral distance (σ = 0.737). The similarity of the two models in term of average residuals is also confirmed by comparing the interevent errors obtained for the two regressions, obtaining very similar values for all earthquakes but the 1911, M 8.2 Kemin event. In particular, different evidences suggest that the magnitude of this event could be overestimated by about half a magnitude unit. Regarding the variability of the residual distribution, all the three considered components (i.e. interevent, interlocation and record-to-record variances) are not negligible, although the largest contribution is related to the record-to-record variability, suggesting that both source and propagation as well as site effects not captured by the considered model influence the spatial variability of the intensity values.
    Description: Published
    Description: 327–337
    Description: JCR Journal
    Description: restricted
    Keywords: Earthquake ground motions ; 05. General::05.01. Computational geophysics::05.01.99. General or miscellaneous
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  • 118
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    Wiley-Blackwell
    In:  EPIC3Oxidative Stress in Aquatic Ecosystems, Abele, D., Zenteno-Savin, T, Vasquez-Medina, J. (Eds) Oxidatve Stress in Aquatic Ecosystems, Blackwell-Wiley., Oxford UK, Wiley-Blackwell, 15 p., pp. 141 -156, ISBN: 978-1-4443-3548-4
    Publication Date: 2019-07-16
    Repository Name: EPIC Alfred Wegener Institut
    Type: Inbook , peerRev
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  • 119
    Publication Date: 2014-04-17
    Description: Compensatory dynamics, overyielding and statistical averaging are mechanisms promoting the temporal stability of natural communities. Using the model of European intertidal rocky shore assemblages and collating 17 datasets, we investigated how the strength of these stability-enhancing mechanisms varies with latitude and how it can be altered by the loss of habitat-formers (e.g. canopy-forming macroalgae). Community stability decreased with increasing latitude, mostly as a consequence of a greater synchronization of species fluctuations. Statistical averaging and overyielding (i.e. richness effects) promoted stability, but their strength did not vary with latitude. The experimental removal of macroalgal canopies caused a strengthening of the statistical averaging effect that was consistent across the latitudinal gradient investigated. Nonetheless, the loss of canopies depressed stability by enhancing the synchronization of species fluctuations on southernmost shores, while it had weak effects on shores at higher latitudes. Variation in life-history traits among canopy-forming species and/or in prevailing environmental conditions across a gradient of latitude could underlie variable effects of habitat-formers on species fluctuations. Our study shows i) that the stability of intertidal assemblages and strength of compensatory dynamics varies with latitude, ii) that canopy-forming macroalgae, exerting a strong control on understorey species, can influence the strength of compensatory dynamics and iii) that biological forcing (i.e. facilitation) can be as important as environmental forcing in enhancing the synchronization of species fluctuations.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
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  • 120
    Publication Date: 2021-12-15
    Description: Some of the most structurally innovative concrete vaults built in imperial Rome employed lightweight volcanic rocks to reduce the lateral thrust on the supporting walls, the most famous being the Pantheon. Roman concrete (opus caementicium) was made up of mortar binding together pieces of large aggregate (caementa) usually ranging from 10 to 20 cm long, which were hand laid in the mortar (as opposed to being poured as is typical in modern concrete), so that it resembles mortared rubble. A key aspect of the development of large-scale concrete vaulting was the ability to regulate the weight of the ingredients in order to reduce the weight of the vaults and to control the forces within the structure. The volcanic environment along the west coast of Italy provided numerous stones of different weights and physical properties from which the builders could choose (Fig. 1), including pumice and scoria, which were the most common choices for the lightweight caementa of the most innovative vaulted structures. Because these materials were produced by many of the Italian volcanoes, our goal was to establish the provenance of those used in vaults in Rome in order to understand better the supply network. We first used thin sections to narrow the potential sources and then we submitted selected samples to X-ray fluorescence
    Description: Published
    Description: 707-727
    Description: JCR Journal
    Description: restricted
    Keywords: concrete vault ; 04. Solid Earth::04.08. Volcanology::04.08.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 121
    Publication Date: 2023-02-10
    Description: The Indonesian island of Sumatra, located in one of the most active zones of the Pacific Ring of Fire, is characterized by a chain of subduction-zone volcanoes which extend the entire length of the island. As a group of volcanic geochemists, we embarked upon a five-week sampling expedition to these exotic, remote, and in part explosive volcanoes (SAGE 2010; Sumatran Arc Geochemical Expedition). We set out to collect rock and gas samples from 17 volcanic centres from the Sumatran segment of the Sunda arc system, with the aim of obtaining a regionally significant sample set that will allow quantification of the respective roles of mantle versus crustal sources to magma genesis along the strike of the arc. Here we document our geological journey through Sumatra’s unpredictable terrain, including the many challenges faced when working on active volcanoes in pristine tropical climes.
    Description: Swedish Science Foundation (VR), Scripps Institution of Oceanography, Istituto Nazionale di Geofisica e Vulcanologia (INGV), Upp-sala University Centre for Natural Disaster Science (CNDS) and Otterborgska donationsfonden
    Description: Published
    Description: 64-70
    Description: 2.3. TTC - Laboratori di chimica e fisica delle rocce
    Description: N/A or not JCR
    Description: restricted
    Keywords: Sumatra ; Indonesia ; geochemisty ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 122
    Publication Date: 2022-05-24
    Description: Series of multiple main shocks that develop on adjacent faults is a typical way in which active extension is accommodated in the Apennines of Italy. This behaviour is explained by fault interaction that occurs at a scale ranging from seconds to days, yielding a space–time clustering of earthquakes, termed as earthquake storms. We show that the seismic energy released by historical earthquakes in central Apennines is clustered into two main small time periods, around 600 and 300 years ago, during which a great portion of the normal faulting belt failed. We favour the hypothesis that clustering results from sudden input of deep fluids into the brittle upper crust. The roughly 300 years periodicity and the 3–4 mm year−1 of tectonic extension suggest that earthquake storms need to be taken into account in seismic hazard scenarios.
    Description: Published
    Description: 300–306
    Description: JCR Journal
    Description: restricted
    Keywords: Apennines ; 04. Solid Earth::04.06. Seismology::04.06.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 123
    Publication Date: 2022-06-08
    Description: Although no deterministic and reliable earthquake precursor is known to date, we are steadily gaining insight into probabilistic forecasting that draws on space–time characteristics of earthquake clustering. Clustering-based models aiming to forecast earthquakes within the next 24 hours are under test in the global project ‘Collaboratory for the Study of Earthquake Predictability’ (CSEP). The 2011 March 11 magnitude 9.0 Tohoku-Oki earthquake in Japan provides a unique opportunity to test the existing 1-day CSEP models against its unprecedentedly active aftershock sequence. The original CSEP experiment performs tests after the catalogue is finalized to avoid bias due to poor data quality. However, this study differs from this tradition and uses the preliminary catalogue revised and updated by the Japan Meteorological Agency (JMA), which is often incomplete but is immediately available. This study is intended as a first step towards operability-oriented earthquake forecasting in Japan. Encouragingly, at least one model passed the test in most combinations of the target day and the testing method, although the models could not take account of the megaquake in advance and the catalogue used for forecast generation was incomplete. However, it can also be seen that all models have only limited forecasting power for the period immediately after the quake. Our conclusion does not change when the preliminary JMAcatalogue is replaced by the finalized one, implying that the models perform stably over the catalogue replacement and are applicable to operational earthquake forecasting. However, we emphasize the need of further research on model improvement to assure the reliability of forecasts for the days immediately after the main quake. Seismicity is expected to remain high in all parts of Japan over the coming years. Our results present a way to answer the urgent need to promote research on time-dependent earthquake predictability to prepare for subsequent large earthquakes in the near future in Japan.
    Description: Published
    Description: 653-658
    Description: 3.1. Fisica dei terremoti
    Description: JCR Journal
    Description: restricted
    Keywords: Time-series analysis ; Probabilistic forecasting ; Seismicity and tectonics ; Computational seismology ; Statistical seismology ; Asia ; 04. Solid Earth::04.06. Seismology::04.06.02. Earthquake interactions and probability
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 124
    Publication Date: 2022-06-10
    Description: A multi-proxy record is presented for approximately the last 4500 cal a BP from Lake Shkodra, Albania/Montenegro. Lithological analyses, C/N ratio and δ13C of the organic and inorganic carbon component suggest that organic matter and bulk carbonate are predominantly authigenic. The δ18O record of bulk carbonate indicates the presence of two prominent wet periods: one at ca. 4300 cal a BP and one at ca. 2500–2000 cal a BP. The latter phase is also found in southern Spain and Central Italy, and represents a prominent event in the western and central Mediterranean. In the last 2000 years, four relatively wet intervals occurred between ca. 1800 and 1500 cal a BP (150–450 AD), 1350–1250 (600–700 AD), 1100–800 (850–1150 AD), and at ca. 90 cal a BP (1860 AD). Between ca. 4100 and 2500 cal a BP δ18O values are relatively high, with three prominent peaks indicating drier conditions at ca. 4100–4000 cal a BP, ca. 3500 and at ca. 3300 cal a BP. Four additional drier events are identified at 1850 (ca. 100 AD), 1400 (ca. 550 AD), 1150 (800 AD) and ca.750 cal a BP (1200 AD). The pollen record does not show changes in accordance with these episodes owing to the poor sensitivity of vegetation in this area, which is dominated by an orographic rainfall effect and where changes in altitudinal vegetation belts do not affect the pollen rain in the lake catchment. However, since ca. 900 cal a BP a significant decrease in the percentage arboreal pollen and in pollen concentrations suggest major deforestation produced by human activities. Copyright © 2012 John Wiley & Sons, Ltd.
    Description: Published
    Description: 780-789
    Description: 3.7. Dinamica del clima e dell'oceano
    Description: JCR Journal
    Description: reserved
    Keywords: Lake Shkodra ; late Holocene ; Mediterranean ; palaeoclimate ; stable isotopes ; 03. Hydrosphere::03.01. General::03.01.06. Paleoceanography and paleoclimatology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 125
    Publication Date: 2022-05-24
    Description: Two different free-air gravity datasets from the Apennines have been analysed in the frequency domain to investigate the mechanisms of support of topography. At short wavelength (λ〈150 km) the best fit between the observed and the calculated admittance gives a value of the elastic thickness of 3.7 km. The observed behaviour of the admittance at larger wavelengths (λ〉150 km) shows that such topography is not supported by elastic stresses in the lithosphere but is dynamically supported by mantle convection. The distribution of gravity anomalies and topography suggests that the mantle is rising beneath the main topographic bulge of the Apennines and that this flow is maintained by buoyancy forces, rather than being driven by movement of the subducted slab.
    Description: Published
    Description: 228-233
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: JCR Journal
    Description: reserved
    Keywords: Dynamic Topography ; Gravity ; Apennines ; 04. Solid Earth::04.03. Geodesy::04.03.03. Gravity and isostasy
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 126
    Publication Date: 2022-05-24
    Description: GPS measurements on Mount St. Helens spanning the 2004.00-2010.85 time interval, encompassing the 2004-2008 dome-building eruption, were analyzed. First, a local reference frame was derived in order to isolate the volcanic ground deformation from the background tectonic pattern related to the interactions between the Pacific, Juan de Fuca and North American plates. Secondly, the resulting ground deformation patterns were modelled to constrain magmatic sources. Results suggest a vertically elongated magma chamber centred at 8 - 9 km depth beneath the summit area that deflated during the beginning of the dome growth and inflated since January 2008, evidencing that a primary magma reservoir was active both during and after the eruption in a magmatic system persistent over the time.
    Description: Published
    Description: 148-155
    Description: 1.3. TTC - Sorveglianza geodetica delle aree vulcaniche attive
    Description: JCR Journal
    Description: restricted
    Keywords: Mount St. Helens ; Ground deformation modelling ; local reference frame ; 05. General::05.02. Data dissemination::05.02.03. Volcanic eruptions
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 127
    Publication Date: 2022-05-24
    Description: The early Cenozoic, which is punctuated by several negative carbon isotope excursions (CIEs), was a time of climatic and oceanographic transition from ’Greenhouse’ to ’Icehouse’ conditions. The occurrence of a 0.5& CIE starting at the top of Chron C27n (TC27N) is reconfirmed with stable isotope data from Zumaia (Spain) and Bjala (Bulgaria) localities. Spectral analysis on respective carbonate ⁄magnetic susceptibility proxy records substantiates the orbital cyclostratigraphy allowing correlation to a high-resolution benthic foraminifera isotope record from ODP Pacific Site 1209, that indicates a coeval 2 C transient warming. The hyperthermal event lasts 200 ka, contrasting with other short-lived events from the Eocene, and displays a relatively rapid onset and a longer tailing back to pre-event values similar to the Palaeocene–Eocene Thermal Maximum (PETM), though lower in amplitude. That a causal trigger for the TC27N event may be the onset of volcanism in the North Atlantic Igneous Province (NAIP) can be inferred from a 200-m-thick lava pile erupted during C27n ⁄ C26r polarity transition in the E Greenland margin.
    Description: Published
    Description: 477-486
    Description: 2.2. Laboratorio di paleomagnetismo
    Description: JCR Journal
    Description: reserved
    Keywords: hyperthermal ; isotope excursion ; TC27N event ; Zumaia ; 03. Hydrosphere::03.01. General::03.01.06. Paleoceanography and paleoclimatology ; 04. Solid Earth::04.04. Geology::04.04.08. Sediments: dating, processes, transport ; 04. Solid Earth::04.04. Geology::04.04.10. Stratigraphy
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 128
    Publication Date: 2022-06-10
    Description: Earthquake forecasts are usually underinformed, and can be plagued by uncertainty in terms of the most appropriate model, and parameter values used in that model. In this paper, we explore the application of two different models to the same seismogenic area. The first is a renewal model based on the characteristic earthquake hypothesis that uses historical/palaeoseismic recurrence times, and fixed rupture geometries. The hazard rate is modified by the Coulomb static stress change caused by nearby earthquakes that occurred since the latest characteristic earthquake. The second model is a very simple earthquake simulator based on plate-motion, or fault-slip rates and adoption of a Gutenberg–Richter magnitude–frequency distribution. This information is commonly available even if historical and palaeoseismic recurrence data are lacking. The intention is to develop and assess a simulator that has a very limited parameter set that could be used to calculate earthquake rates in settings that are not as rich with observations of large-earthquake recurrence behaviour as the Nankai trough. We find that the use of convergence rate as a primary constraint allows the simulator to replicate much of the spatial distribution of observed segmented rupture rates along the Nankai, Tonankai and Tokai subduction zones. Although we note rate differences between the two forecast methods in the Tokai zone, we also see enough similarities between simulations and observations to suggest that very simple earthquake rupture simulations based on empirical data and fundamental earthquake laws could be useful forecast tools in information-poor settings.
    Description: Published
    Description: 1673-1688
    Description: 3.1. Fisica dei terremoti
    Description: JCR Journal
    Description: restricted
    Keywords: Time series analysis ; Spatial analysis ; Probability distributions ; Seismic cycle ; Earthquake interaction ; forecasting, and prediction ; Statistical seismology. ; 04. Solid Earth::04.06. Seismology::04.06.02. Earthquake interactions and probability ; 04. Solid Earth::04.06. Seismology::04.06.05. Historical seismology ; 04. Solid Earth::04.07. Tectonophysics::04.07.05. Stress
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 129
    facet.materialart.
    Unknown
    Wiley-Blackwell
    In:  EPIC3Oxidative Stress in Aquatic Ecosystems, Oxidative Stress in Aquatic Ecosystems, Wiley-Blackwell, 18 p., pp. 263-280, ISBN: 978-1-4443-3548-4
    Publication Date: 2023-06-21
    Description: The chapter will summarize and critically review metabolic responses to environmental stress and stress effects on energy budgets in mollusks. Metabolic adaptations to environmental stress will be analyzed including alternative energy conserving pathways, aerobic/anaerobic transitions and metabolic arrest. Their role in the efficient use of energy substrates and in the maintenance of cellular homeostasis and redox status will be discussed. General stress effects on energy budget at different organization levels (from the cell to the whole-organism) will be analyzed including energy uptake, assimilation, conversion and expenditure, as well as the metabolic costs associated with stress resistance (including antioxidant protection, chaperone function and damage repair). We will compare metabolic responses to moderate and extreme levels of environmental stressors using temperature, ocean acidification, salinity, oxygen deficiency and toxic metal stress as examples. This chapter will also outline the future research directions to improve our understanding of the stress effects on bioenergetics in mollusks and other invertebrates. Keywords: Stress, metabolic adaptation, metabolic arrest, bioenergetics, cellular defense, energy trade-offs
    Repository Name: EPIC Alfred Wegener Institut
    Type: Inbook , peerRev
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  • 130
    facet.materialart.
    Unknown
    Wiley-Blackwell
    In:  EPIC3Wiley-Blackwell, ISBN: 9781444335484
    Publication Date: 2023-06-21
    Repository Name: EPIC Alfred Wegener Institut
    Type: Book , peerRev
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  • 131
    facet.materialart.
    Unknown
    Wiley-Blackwell
    In:  EPIC3Oxidative Stress in Aquatic Ecosystems, Oxidative Stress in Aquatic Ecosystems, Oxford, Wiley-Blackwell, 524 p., pp. 115-126, ISBN: 978 1 4443 3548 4
    Publication Date: 2023-06-21
    Repository Name: EPIC Alfred Wegener Institut
    Type: Inbook , peerRev
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  • 132
    Publication Date: 2021-06-08
    Description: We investigated the high frequency attenuation of S-waves in Southeastern Alps and Northern External Dinarides using waveforms from 331 earthquakes (3.0〈 Mw〈 6.5). The spectral decay parameter, k, was computed using 1345 three component high quality records, collected by the Italian Strong Motion Network (RAN) and by the Short-Period Seismometric Network of North-Eastern Italy (NEI) in the period 1976-2007. Weak motion data from 11 stations of the NEI network and strong motion data collected by 5 accelerometers of the RAN were analyzed. The k parameter was estimated in the 0-250 Km distance range, in a frequency band extending from the corner frequency of the event up to 25 or 45 Hz, using the amplitude acceleration Fourier spectra of S-waves. The observed record-to-record variability of k was modeled by applying a generalized inversion procedure, using both parametric and non-parametric approaches. Our results evidence that k is independent on earthquake size, while it shows both site and distance dependence. Stations of the NEI network present the same increase of k with epicentral distance, Re, and show values of the zero-distance k parameter, k0(S), between 0.017 and 0.053 s. For the whole region, the k increase with distance can be described through a linear model with slope dk/dRe = (1.4±0.1)x10^(-4) s/Km. Assuming an average S-wave velocity, 〈Vs〉=3.34 Km/s between 5 and 15 Km depth, we estimate an average frequency independent quality factor, 〈Qi〉=2140, for the corresponding crustal layer. The non-parametric approach evidences a weak positive concavity of the curve that describes the k increase with Re at about 90 Km distance. This result can be approximated through a piecewise linear function with slopes of 1.0x10^(-4) s/Km and 1.7x10^(-4) s/Km, in accordance with a three layers model where moving from the intermediate to the bottom layer both 〈Qi〉 and 〈Vs〉 decrease. Two regional dependences were found: data from earthquakes located westward to the NEI network evidence weaker attenuation properties, probably because of S-wave reflections from different part of the Moho discontinuity under the eastern Po Plain, at about 25-30 Km depth, while earthquakes located eastward (in western Slovenia), where the Moho deepens up to 45-50 Km, evidence a higher attenuation. Moreover, the k estimates obtained with data from earthquakes located in the area of the 1998 (Mw=5.7) and 2004 (Mw=5.2) Kobarid events are 0.017 s higher than the values predicted for the whole region, probably because of the high level of fracturing that characterizes fault zones. The comparison between measured and theoretical values of k, computed at a few stations with available S-wave velocity profiles, reveals that the major contribution to the total k0(S) is due to the sedimentary column (from surface to 800 m depth). The hard rock section contribution is limited to 0.005 s, in accordance with a maximum contribution of 0.010 s predicted by the non-parametric inversion.
    Description: Published
    Description: 1393-1416
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: JCR Journal
    Description: open
    Keywords: Earthquake source observations ; Body waves ; Seismic attenuation ; Site effects ; Wave propagation ; 04. Solid Earth::04.06. Seismology::04.06.04. Ground motion
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 133
    Publication Date: 2021-06-07
    Description: We present a high-resolution palaeomagnetic and rock magnetic study of two cores, MS06 and MS06-SW (6.7 and 1.1 m long, respectively), collected at 72 m below sea level in the Augusta Bay shelf (Eastern Sicily, Ionian Sea, Italy) about 2.3 kmfrom the coastline. Geophysical surveying carried out in the sampling area highlighted the presence of a homogeneous sedimentary sequence that most likely was deposited after the Last Glacial Maximum and was not affected by anthropogenic disturbances. The two cores penetrated a monotonous mud sedimentary sequence, interrupted at ∼3 m depth by a 3–4-cm-thick volcanic sandy layer that is correlated with the tephra fallout deposit produced by the 122 BC plinian eruption of Mt Etna. This tephra, along with radiocarbon dating of nine marine shells and with radioactive tracers for the uppermost 0.3 m (210Pb and 137Cs), provide the chronological constraints for the stratigraphic sequence that resulted younger than 4500 yr BP. Palaeomagnetic and rock magnetic data show that the sample sequence is magnetically homogeneous. A single peak of high magnetic mineral concentration is present and corresponds to the volcanic sandy layer. Palaeomagnetic data allowed the identification of a well-defined characteristic remanent magnetization that provides a high-resolution record of palaeosecular variation (PSV) at the sampling site. The reconstructed PSV curve is in good agreement with the available regional reference PSV curves and with the prediction from recent PSV modelling for Europe. The palaeomagnetic data obtained in this study on the one hand support and refine the age model for the cores, derived from other independent constraints, and on the other hand provide an original high-resolution PSV curve that can serve as a reference for the central Mediterranean over the last 4 ka.
    Description: Published
    Description: 191 - 202
    Description: 2.2. Laboratorio di paleomagnetismo
    Description: JCR Journal
    Description: restricted
    Keywords: Palaeointensity ; Palaeomagnetic secular variation ; Marine magnetics and palaeomagnetics ; Europe ; 04. Solid Earth::04.05. Geomagnetism::04.05.02. Geomagnetic field variations and reversals ; 04. Solid Earth::04.05. Geomagnetism::04.05.06. Paleomagnetism
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 134
    Publication Date: 2017-04-04
    Description: The connection between Tropical Pacific and North Pacific variability is investigated in a state-of-the art coupled ocean-atmosphere model, comparing two 20th century simulations at T30 and T106 atmospheric horizontal resolutions. Despite a better simulation of the frequency and the spatial distribution of the Tropical Pacific anomalies associated with the El Nino Southern Oscillation (ENSO) in the high-resolution experiment, the response in the North Pacific is scarcely different from the low-resolution experiment where the ENSO variability is weaker and at higher than observed frequency. In the North Pacific, the response of surface atmospheric fields to the variability in the Tropical Pacific appears to be affected by local coupling processes significantly different in the two experiments. The coupling between sea level pressure (SLP) and sea surface temperature (SST) in the North Pacific as well as the influence of the Tropical Pacific SST has been measured here by means of the ‘coupled manifold’ technique. In the low-resolution case the SLP variances linked to the fraction of North Pacific SST not influenced by the Tropical Pacific are weak suggesting that the remote influence is strong, consistently with the observations. On the contrary, in the high-resolution experiment the fractions and the patterns of the SLP variances due to the Tropical Pacific SST and those linked to the North Pacific SST are comparable. In the latter case, model systematic errors in the northwestern Pacific influences the local coupling processes thus triggering the remote response. We conclude that an increased atmospheric horizontal resolution does not reduce the coupled model systematic errors in the representation of the teleconnection between the North and the Tropical Pacific and that the validation of coupled models has to consider both remote and local processes.
    Description: Published
    Description: 1640-1653
    Description: 3.7. Dinamica del clima e dell'oceano
    Description: JCR Journal
    Description: open
    Keywords: Tropical Pacific-North Pacific teleconnection ; ENSO ; coupled GCMs ; 01. Atmosphere::01.01. Atmosphere::01.01.02. Climate ; 01. Atmosphere::01.01. Atmosphere::01.01.04. Processes and Dynamics ; 03. Hydrosphere::03.01. General::03.01.03. Global climate models
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 135
    Publication Date: 2017-04-04
    Description: Edifice instability, that can result in catastrophic flank collapse, is a fundamental volcanic hazard. The subvolcanic basement can encourage such instability, especially if it is susceptible to mechanical weakening by devolatilization reactions near magmatic temperatures. For this reason, understanding how the physical and chemical properties of representative lithologies deteriorate at high temperatures is potentially highly relevant for volcanic hazard mitigation. This is particularly true for sedimentary rock, commonly found underlying volcanic edifices worldwide, that undergo rapid deterioration even under modest temperatures. Therefore, here we present the first experimental study of devolatilization reactions, induced by magmatic temperatures, on sedimentary rock comprising a subvolcanic basement. Our results show that, for a marly limestone representative of the basement at Mt Etna, devolatilization reactions, namely the dehydroxylation of clay minerals and the decarbonation of calcium carbonate, result in a dramatic reduction of mechanical strength and seismic velocities. These temperature-driven reactions can promote volcanic instability at stresses much lower than previously estimated.
    Description: Published
    Description: 1073–1077
    Description: 2.3. TTC - Laboratori di chimica e fisica delle rocce
    Description: JCR Journal
    Description: reserved
    Keywords: Phase transitions ; Experimental volcanism ; 04. Solid Earth::04.01. Earth Interior::04.01.04. Mineral physics and properties of rocks
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 136
    Publication Date: 2017-04-03
    Description: With the continued growth in availability of DInSAR and GPS data, space based geodesy has been widely applied to image the coseismic displacement field and to retrieve the static dislocation over the fault plane for almost all the significant earthquakes of the past two decades. This is performed by linear data inversion over a set of subfaults, generally characterized by a constant and predefined or manually adjusted dimensions. In this paper we propose a new algorithm to automatically retrieve an optimized fault subdivision in the linear inversion of coseismic geodetic data. The code iteratively keeps the parameter resolution close to a predefined high value. We first discuss the rationale supporting our algorithm and, after a detailed description of its implementation, we analyze the advantages of its introduction in the data inversion. The algorithm was tested against an exhaustive range of synthetic and real datasets and fault mechanisms. Among them, we present the results for the Mw 6.2, 2009 L’Aquila (Central Italy) earthquake and compare the new and previously published slip distributions showing the disappearance of misleading slip pattern and the increased resolution for shallower zones.
    Description: Published
    Description: 529-538
    Description: 1.10. TTC - Telerilevamento
    Description: JCR Journal
    Description: open
    Keywords: fault modelling ; geodetic data inversion ; 04. Solid Earth::04.03. Geodesy::04.03.07. Satellite geodesy
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 137
    Publication Date: 2017-04-04
    Description: The 2009 April 6, Mw= 6.3 L’Aquila earthquake occurred within a complex system of NW–SE trending normal faults in the Abruzzi Central Apennines (Italy). We analyse the coseismic deformation as measured by 〉70 global positioning system (GPS) stations, both from continuous and survey-mode networks, providing unprecedented details for a moderate normal faulting earthquake in Italy from GPS measurements. We use rectangular, uniform-slip, dislocations embedded in an elastic, homogeneous and isotropic half-space and a constrained, non-linear optimization algorithm, to solve for the best-fitting rectangular dislocation geometry and coseismic-slip distribution. We use a bootstrap approach to investigate uncertainties in the model parameters and define confidence bounds for all the inverted parameters. The rupture occurred on a N129°E striking and 50° southwestward dipping normal fault, in agreement with geological observations of surface breaks along the Paganica fault. Our distributed slip model exhibits a zone of relatively higher slip (〉60 cm) between ∼1.5 and ∼11 km depth, along a roughly downdip, NW–SE elongated patch, confined within the fault plane inverted assuming uniform-slip. The highest slip, of the order of ∼1 m, occurred on a ∼16 km2 area located at ∼5 km depth, SE of the mainshock epicentre. The analysis of model resolution suggests that slip at depth below ∼5 km can be resolved only at a spatial scale larger than 2 km, so a finer discretization of different asperities within the main patch of coseismic-slip is not allowed by GPS data. We compute the coseismic Coulomb stress changes in the crustal volume affected by the major aftershocks, and compare the results obtained from the uniform-slip and the heterogeneous-slip models. We find that most of the large aftershocks occurred in areas of Coulomb stress increase of 0.2–13 bar and that a deepening of the slip distribution down to a depth greater than 6 km in the SE part of the fault plane, in agreement with the inverted slip model, can explain the deepest, April 7, Mw 5.3 aftershock.
    Description: Published
    Description: 473-489
    Description: 1.9. Rete GPS nazionale
    Description: 3.2. Tettonica attiva
    Description: JCR Journal
    Description: reserved
    Keywords: Satellite geodesy ; Space geodetic surveys ; Earthquake ground motions ; Earthquake source observations ; Earthquake interaction, forecasting, and prediction ; 04. Solid Earth::04.03. Geodesy::04.03.01. Crustal deformations ; 04. Solid Earth::04.03. Geodesy::04.03.07. Satellite geodesy ; 04. Solid Earth::04.06. Seismology::04.06.01. Earthquake faults: properties and evolution ; 04. Solid Earth::04.06. Seismology::04.06.02. Earthquake interactions and probability ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 138
    Publication Date: 2017-04-04
    Description: We analyzed a broad region around L’Aquila in search of seismogenic faults similar to that responsible for the 6 April 2009 earthquake (Mw 6.3). Having the lessons learned from this earthquake in mind, we focused on adjacent areas displaying similar morphotectonic, geological and structural evidence. The basin running from Barisciano to Civitaretenga-Navelli, notably located near the southeastern edge of the 2009 aftershock pattern, appears to be one of such areas. We collected morphotectonic and structural data indicating that this basin is underlain by a major active normal fault (San Pio Fault). All the observations are very much reminiscent of the morphotectonic, geological and structural setting of area struck by the L’Aquila earthquake, suggesting that the newly identified fault has the potential for a Mw 6.2-6.4 shock.
    Description: Published
    Description: Pages: 108–115
    Description: 3.2. Tettonica attiva
    Description: JCR Journal
    Description: partially_open
    Keywords: Seismotectonics ; Morphotectonics ; Active fault ; San Pio basin ; 04. Solid Earth::04.04. Geology::04.04.01. Earthquake geology and paleoseismology ; 04. Solid Earth::04.04. Geology::04.04.03. Geomorphology ; 04. Solid Earth::04.04. Geology::04.04.09. Structural geology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 139
    Publication Date: 2019-12-03
    Description: The aerosol climatology at the coastal Antarctic Neumayer Station (NM) was investigated based on continuous, 25 years long observations of biogenic sulfur components (methanesulfonate and non sea salt sulfate), sea salt and nitrate. Whilst significant long-term trends could only be detected for nitrate (-3.6±2.5% per year between 1983 and 1993 and +4.0±3.2% per year from 1993-2007), non-harmonic periodicities between 2 and 5 years were typical for all species. Dedicated time series analyses revealed that relations to sea ice extent and various circulation indices are weak at best or not significant. In particular, no consistent link between sea ice extent and sea salt loadings was evident suggesting only a rather local relevance of the NM sea salt record. Nevertheless, a higher Southern Annular Mode index tended to entail a lower biogenic sulfur signal. In examining the spatial uniformity of the NM findings we contrasted them to respective 17 years records from the coastal Dumont d’Urville Station (DDU). We found similar long term trends for nitrate, indicating an Antarctic-wide but not identifiable atmospheric signal, though any significant impact of solar activity or pollution could be ruled out. No inter-site variability on the multi annual scale was evident for the other ionic compounds.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
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  • 140
    Publication Date: 2019-12-03
    Description: We investigated the variability of 210Pb, 7Be and 10Be in coastal Antarctica aerosol samples based on continuous, monthly and annually resolved time series which we obtained from Neumayer Station over the period 1983 to 2008. Clear seasonal cycles peaking in the local summer half year stands out in being common to all three radionuclide records. However, MC-SSA time series analyses suggest that significant multi-annual changes are confined to a 4-5 years periodicity resembling that of the SAM circulation index in case of 210Pb and to the expected solar decadal cycle in case of the cosmogenic Be-isotopes. Both, changes in the meridional transport and surface inversion strength appear to drive the seasonal 210Pb cycle which generally peaks in November. In contrast, stratospheric air mass intrusion are proved to be the main reason for the Be-isotopes seasonality as revealed by enhanced 10Be/ 7Be ratios occurring broadly concurrently with the individual Be-isotopes and the 7Be/210Pb ratios during late summer/early autumn. Although both, the (annual) 10Be and the monthly 7Be records reflects the decadal solar modulated production signal the detailed pattern of their decadal changes essentially deviate for unknown reasons, though a substantial excess 7Be production by solar energetic particles could be ruled out.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
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  • 141
    Publication Date: 2017-04-04
    Description: During the MW 5.7 and 6.0 Umbria–Marche earthquakes of 1997 September 26, the historical centre of Nocera Umbra suffered MCS intensity VII–VIII. The zone is located on the top of a hill, a condition potentially favourable to ground motion amplification. However, also vulnerability is higher on the hill because of the ancient age of buildings. A temporary array of eight seismological stations was installed across the hill to quantify the amplification effect due to topography.Waveforms of 14 aftershocks (2.6〈ML 〈4.1) are selected for the analysis. During each earthquake the largest amplitudes are observed on the hilltop, spectral ratios are computed using rotated horizontal components to search for directional effects. Amplifications are found in two separate frequency bands: one in the range 2–4 Hz, where the increase of amplitude is moderate (never exceeding a factor of 4) and the polarization is transversal to the hill major axis; the second above 10 Hz, where amplifications are larger and reach values as high as 25 Hz. High-frequency polarization varies for different sites and frequencies suggesting that smaller-scale complexities control the high frequency response. Synthetic seismograms of 2-D models confirm the occurrence of amplification, although not all details are fit by numerical simulations and the agreement between observations and models is significant only in terms of the fundamental resonance frequency, around 3 Hz. In the models, amplifications are much smaller than the observed ones. We conclude that topography could have been responsible for a small increase of damage in the hill zone but the most significant role on damage was played by the locally higher vulnerability.
    Description: Published
    Description: 977-987
    Description: 4.1. Metodologie sismologiche per l'ingegneria sismica
    Description: JCR Journal
    Description: reserved
    Keywords: Earthquake ground motion ; Site effects ; 04. Solid Earth::04.06. Seismology::04.06.04. Ground motion
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 142
    Publication Date: 2021-11-09
    Description: The shallow subsurface structure of the 2009 April 6 Mw 6.3 L’Aquila earthquake surface rupture at Paganica has been investigated with ground penetrating radar to study how the surface rupture relates spatially to previous surface displacements during the Holocene and Pleistocene. The discontinuous surface rupture stepped between en-echelon/parallel faults within the overall fault zone that show clear Holocene/Pleistocene offsets in the top 10 m of the subsurface. Some portions of the fault zone that show clear Holocene offsets were not ruptured in 2009, having been bypassed as the rupture stepped across a relay zone onto a fault across strike. The slip vectors, defined by opening directions across surface cracks, indicate dip-slip normal movement, whose azimuth remained constant between 210◦ and 228◦ across the zone where the rupture stepped between faults. We interpret maximum vertical offsets of the base of the Holocene summed across strike to be 4.5 m, which if averaged over 15 kyr, gives a maximum throw-rate of 0.23–0.30 mm yr–1, consistent with throw-rates implied by vertical offsets of a layer whose age we assume to be ∼33 ka. This compares with published values of 0.4 mm yr–1 for a minimum slip rate implied by offsets of Middle Pleistocene tephras, and 0.24 mm yr–1 since 24.8 kyr from palaeoseismology. The Paganica Fault, although clearly an important active structure, is not slipping fast enough to accommodate all of the 3–5 mm yr–1 of extension across this sector of the Apennines; other neighbouring range-bounding active normal faults also have a role to play in the seismic hazard.
    Description: Published
    Description: 774–790
    Description: 3.2. Tettonica attiva
    Description: JCR Journal
    Description: open
    Keywords: Ground penetration radar ; Aquila earthquake ; extension ; active tectonics ; 04. Solid Earth::04.06. Seismology::04.06.01. Earthquake faults: properties and evolution
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 143
    Publication Date: 2017-04-04
    Description: Prominent arrivals in the coda of seismograms from the wider Alpine area can be associated with lateral reflections of Love waves at the northern Apennines mountain chain (Italy), where structural heterogeneity causes an abrupt contrast in phase velocity. We discuss an approach to image lateral heterogeneity from reflected surface waves using intermediate-period, three- component coda waveforms as sources for an adjoint wavefield that propagates the reflections backward in time. We numerically compute three-dimensional sensitivity kernels for the dependence of coda waveforms on P velocity, S velocity and density, based upon correlations between the adjoint and the regular forward wavefields. We consider synthetic coda waveforms for a simplified model of the northern Apennines, as well as real coda observations from five moderate magnitude earthquakes (M W 4.6–5.6) in the southern Alps. Wave propagation is simulated using the spectral-element method, for which a 3-D regional earth model is used in the case of real data. Single and combined event sensitivity kernels provide clear images of the reflectivity associated with the northern Apennines in kernels for density and S-wave speed. The kernels show that surface wave reflections occur near the axial zone of the mountain chain. Apart from the Apennines, the approach is able to image other smaller reflectivity patches from the coda waveforms, like the Ivrea zone in the southern Alps. Our coda misfit kernels can be integrated in a gradient-based waveform tomography, where they could enhance the shar pness of the model at lateral discontinuities.
    Description: Published
    Description: 543–554
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: JCR Journal
    Description: reserved
    Keywords: Tomography; ; Computational seismology ; Wave scattering and diffraction ; Crustal structure ; 04. Solid Earth::04.06. Seismology::04.06.07. Tomography and anisotropy
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 144
    Publication Date: 2017-04-04
    Description: Stick-slip dynamic instability is a key mechanism governing frictional processes from microscale physics to earthquake faults and landslides; yet challenging questions are stil open about its nucleation and propagation dynamics. We present novel observations on laboratory experimental faults where spontaneously nucleating fractures are produced, describing (1) an initial quasistatic, stable rupture front accelerating to subshear and then intersonic velocity; 2) the arisal of a higher degree of complexity when the friction to prestress ratio is increased on the sliding surface. The complex behaviour includes stop and go sequences, irregular proportion and rerupturing episodes within short-time intervals, implying rapid restrengthening of the surface and the formation of self-healing pulses, reproducing experimentally for the first time a behaviour observed on seismic faults.
    Description: Published
    Description: 697-702
    Description: 2.3. TTC - Laboratori di chimica e fisica delle rocce
    Description: 3.1. Fisica dei terremoti
    Description: JCR Journal
    Description: reserved
    Keywords: Fractures and flow; friction; earthquake dynamics; Dynamics and mechanics of faulting ; 04. Solid Earth::04.04. Geology::04.04.06. Rheology, friction, and structure of fault zones
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 145
    Publication Date: 2017-04-04
    Description: The Montalbano Jonico (MJ) section, cropping out in Southern Italy, represents a potential candidate to define the Lower/Middle Pleistocene boundary and it has been proposed as a suitable Global Stratotype Section and Point (GSSP) of the Ionian Stage (Middle Pleistocene). The MJ section is the only continuous benthic and planktonic δ18O on-land reference in the Mediterranean area for the Mid-Pleistocene transition, spanning an interval between about 1240 and 645 ka. Combined biostratigraphy and sapropel chronology, tephra stratigraphy and complete high-resolution benthic and planktonic foraminiferal stable oxygen isotope records already provide a firm chronostratigraphic framework for the MJ section. However, magnetostratigraphy was still required to precisely locate the Brunhes-Matuyama transition and to mark the GSSP for the Ionian stage. We carried out a palaeomagnetic study of a subsection (Ideale section) of the MJ composite section, sampling 61 oriented cores from 56 stratigraphic levels spread over a ca. 80-m-thick stratigraphic interval that correlates to the oxygen isotopic stage 19 and should therefore include the Brunhes-Matuyama reversal. The palaeomagnetic data indicate a stable and almost single-component natural remanent magnetization (NRM). A characteristic remanent magnetization (ChRM) was clearly identified by stepwise demagnetization of the NRM. The ChRM declination values vary around 0◦ and the ChRM inclination around the expected value (59◦) for a geocentric axial dipole field at the sampling locality. This result indicates that the section has been remagnetized during the Brunhes Chron. A preliminary study of 27 additional not azimuthally oriented hand samples, collected at various levels from other parts of the MJ composite section, indicates that all the samples are of normal polarity and demonstrates that the remagnetization is widespread across the whole exposed stratigraphic sequence. A series of specific rock magnetic techniques were then applied to investigate the nature of the main magnetic carrier in the study sediments, and they suggest that the main magnetic mineral in the MJ section is the iron sulphide greigite (Fe3S4). Scanning electron microscope observations and elemental microanalysis reveal that greigite occurs both as individual euhedral crystals and in iron sulphides aggregates filling voids in the clay matrix. Therefore, we infer that the remagnetization of the section is due to the late-diagenetic growth of greigite under reducing conditions, most likely resulting in the almost complete dissolution of the original magnetic minerals. Iron sulphide formation in the MJ section can be linked to migration of mineralized fluids. Our inferred timing of the remagnetization associated with greigite growth represents the longest remanence acquisition delay documented in greigite-bearing clays of the Italian peninsula so far.
    Description: In press
    Description: 2.2. Laboratorio di paleomagnetismo
    Description: JCR Journal
    Description: open
    Keywords: Remagnetization ; 04. Solid Earth::04.05. Geomagnetism::04.05.06. Paleomagnetism ; 04. Solid Earth::04.05. Geomagnetism::04.05.07. Rock magnetism
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 146
    Publication Date: 2017-04-04
    Description: We present a high-resolution palaeomagnetic and rock magnetic study of two cores, MS06 and MS06-SW (6.7 and 1.1 m long, respectively), collected at 72 m below sea level in the Augusta Bay shelf (Eastern Sicily, Ionian Sea, Italy) about 2.3 kmfrom the coastline. Geophysical surveying carried out in the sampling area highlighted the presence of a homogeneous sedimentary sequence that most likely was deposited after the Last Glacial Maximum and was not affected by anthropogenic disturbances. The two cores penetrated a monotonous mud sedimentary sequence, interrupted at ∼3 m depth by a 3–4-cm-thick volcanic sandy layer that is correlated with the tephra fallout deposit produced by the 122 BC plinian eruption of Mt Etna. This tephra, along with radiocarbon dating of nine marine shells and with radioactive tracers for the uppermost 0.3 m (210Pb and 137Cs), provide the chronological constraints for the stratigraphic sequence that resulted younger than 4500 yr BP. Palaeomagnetic and rock magnetic data show that the sample sequence is magnetically homogeneous. A single peak of high magnetic mineral concentration is present and corresponds to the volcanic sandy layer. Palaeomagnetic data allowed the identification of a well-defined characteristic remanent magnetization that provides a high-resolution record of palaeosecular variation (PSV) at the sampling site. The reconstructed PSV curve is in good agreement with the available regional reference PSV curves and with the prediction from recent PSV modelling for Europe. The palaeomagnetic data obtained in this study on the one hand support and refine the age model for the cores, derived from other independent constraints, and on the other hand provide an original high-resolution PSV curve that can serve as a reference for the central Mediterranean over the last 4 ka.
    Description: In press
    Description: 2.2. Laboratorio di paleomagnetismo
    Description: JCR Journal
    Description: restricted
    Keywords: Palaeomagnetic secular variation ; Palaeointensity ; Marine magnetics and palaeomagnetics ; Europe ; 04. Solid Earth::04.05. Geomagnetism::04.05.02. Geomagnetic field variations and reversals ; 04. Solid Earth::04.05. Geomagnetism::04.05.06. Paleomagnetism
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 147
    Publication Date: 2017-04-04
    Description: We map the b-value in the subduction zone of theWellington region, NewZealand, using a high quality earthquake catalogue relocated with a 3-D seismic velocity model, consisting of 50 314 events that occurred between 1990 and 2005. In order to investigate heterogeneity in the crust of the overlying plate and in the upper plane of the Wadati–Benioff Zone (WBZ), we analyse a series of cross-sections perpendicular to the strike of the subduction zone. We calculate the b-values selecting events with magnitude of completeness ≥2.4 and depth ≤65 km and projecting the seismicity within 20 km on each side of the cross-sectional planes. We observe areas of high b-value (∼1.7) near the plate interface and regions of low b-value anomalies are detected both in the WBZ in the northwest region below 40 km depth and in the overlying plate in the northern South Island at 10 km depth. The anomalies are statistically significant based on Utsu’s p-test and the bootstrap method and are not data processing method or parameter dependent. We compare the b-value distribution with previously determined 3-D distributions of Vp, Vp/Vs andQp from seismic tomography. This comparison suggests that material inhomogeneity, caused by fluid filled cracks resulting from dehydration of the subducted slab and subducted sediments, is the predominant cause of b-value variation in the shallow part of this subduction zone. Our observations are consistent with a previously proposed conceptual model that fluid distribution in the shallow part of this subduction zone is controlled by the permeability of geological terranes in the overlying plate.
    Description: Published
    Description: 451-460
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: JCR Journal
    Description: restricted
    Keywords: Seismic attenuation ; Seismic tomography ; Statistical seismology ; Subduction zone processes ; 04. Solid Earth::04.06. Seismology::04.06.07. Tomography and anisotropy ; 05. General::05.01. Computational geophysics::05.01.04. Statistical analysis
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 148
    Publication Date: 2017-04-04
    Description: The axial zone of the Apenninic belt in central Italy is a tectonically active region affected by post-orogenic Quaternary extension. The present-day stress field is characterized by a minimum horizontal stress (Shmin) ∼ NE–SW oriented, derived mainly from earthquake focal mechanisms and secondarily from borehole breakouts and fault data. The paper describes the computation of the Shmin orientation along two deep boreholes located in the vicinity of the area hit by the 2009 April 6, Mw 6.3 L’Aquila earthquake. The analysed wells show breakout zones at a depth range between 1.4 and 4.6 km, giving precious information on a depth interval usually not investigated by any other data. The results show an Shmin N81 ± 22◦ and N74 ± 10◦ oriented for Varoni 1 and Campotosto 1 wells, respectively. The comparison among the breakouts, the 2009 seismic sequence, the past seismicity and the Quaternary faults indicates a small rotation of Shmin orientation from ∼ NE, in the southern, to ∼ ENE in the northern sector of the study area, where the wells are located. These differences are linked both to the natural variations of data and to the orientation of the main tectonic structures varying from NW–SE in the Abruzzi region to ∼ N–S moving toward the Umbro-Marchean Apennines. The identification of constant Shmin orientations with depth derived from all the examined active stress data, confirms the breakouts as reliable stress indicators also for aseismic areas.
    Description: Published
    Description: 3.2. Tettonica attiva
    Description: JCR Journal
    Description: reserved
    Keywords: Seismicity and tectonics ; present-day stress ; borehole breakouts ; Italy ; 04. Solid Earth::04.07. Tectonophysics::04.07.05. Stress
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 149
    Publication Date: 2021-09-03
    Description: The Montalbano Jonico (MJ) section, cropping out in Southern Italy, represents a potential candidate to define the Lower/Middle Pleistocene boundary and it has been proposed as a suitable Global Stratotype Section and Point (GSSP) of the Ionian Stage (Middle Pleistocene). The MJ section is the only continuous benthic and planktonic δ18O on-land reference in the Mediterranean area for the Mid-Pleistocene transition, spanning an interval between about 1240 and 645 ka. Combined biostratigraphy and sapropel chronology, tephra stratigraphy and complete high-resolution benthic and planktonic foraminiferal stable oxygen isotope records already provide a firm chronostratigraphic framework for the MJ section. However, magnetostratigraphy was still required to precisely locate the Brunhes-Matuyama transition and to mark the GSSP for the Ionian stage. We carried out a palaeomagnetic study of a subsection (Ideale section) of the MJ composite section, sampling 61 oriented cores from 56 stratigraphic levels spread over a ca. 80-m-thick stratigraphic interval that correlates to the oxygen isotopic stage 19 and should therefore include the Brunhes-Matuyama reversal. The palaeomagnetic data indicate a stable and almost single-component natural remanent magnetization (NRM). A characteristic remanent magnetization (ChRM) was clearly identified by stepwise demagnetization of the NRM. The ChRM declination values vary around 0◦ and the ChRM inclination around the expected value (59◦) for a geocentric axial dipole field at the sampling locality. This result indicates that the section has been remagnetized during the Brunhes Chron. A preliminary study of 27 additional not azimuthally oriented hand samples, collected at various levels from other parts of the MJ composite section, indicates that all the samples are of normal polarity and demonstrates that the remagnetization is widespread across the whole exposed stratigraphic sequence. A series of specific rock magnetic techniques were then applied to investigate the nature of the main magnetic carrier in the study sediments, and they suggest that the main magnetic mineral in the MJ section is the iron sulphide greigite (Fe3S4). Scanning electron microscope observations and elemental microanalysis reveal that greigite occurs both as individual euhedral crystals and in iron sulphides aggregates filling voids in the clay matrix. Therefore, we infer that the remagnetization of the section is due to the late-diagenetic growth of greigite under reducing conditions, most likely resulting in the almost complete dissolution of the original magnetic minerals. Iron sulphide formation in the MJ section can be linked to migration of mineralized fluids. Our inferred timing of the remagnetization associated with greigite growth represents the longest remanence acquisition delay documented in greigite-bearing clays of the Italian peninsula so far.
    Description: Published
    Description: 1049-1066
    Description: 2.2. Laboratorio di paleomagnetismo
    Description: 2.3. TTC - Laboratori di chimica e fisica delle rocce
    Description: JCR Journal
    Description: reserved
    Keywords: Magnetostratigraphy ; Remagnetization ; Rock and mineral magnetization ; 04. Solid Earth::04.05. Geomagnetism::04.05.06. Paleomagnetism ; 04. Solid Earth::04.05. Geomagnetism::04.05.07. Rock magnetism
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  • 150
    Publication Date: 2021-06-22
    Description: In this work, we analyse continuous measurements of microseisms to assess the reliability of the fundamental resonance frequency estimated by means of the horizontal-to-vertical (H/V) spectral ratio within the 0.1–1 Hz frequency range, using short-period sensors (natural period of 1 s). We apply the H/V technique to recordings of stations installed in two alluvial basins with different sedimentary cover thicknesses—the Lower Rhine Embayment (Germany) and the Gubbio Plain (Central Italy). The spectral ratios are estimated over the time–frequency domain, and we discuss the reliability of the results considering both the variability of the microseism activity and the amplitude of the instrumental noise. We show that microseisms measured by short period sensors allow the retrieval of fundamental resonance frequencies greater than about 0.1–0.2 Hz, with this lower frequency bound depending on the relative amplitude of themicroseism signal and the self-noise of the instruments. In particular,we show an examplewhere the considered short-period sensor is connected to instruments characterized by an instrumental noise level which allows detecting only fundamental frequencies greater than about 0.4 Hz. Since the frequency at which the peak of the H/V spectral ratio is biased depends upon the seismic signal-to-instrument noise ratio, the power spectral amplitude of instrumental self-noise should be always considered when interpreting the frequency of the peak as the fundamental resonance frequency of the investigated site.
    Description: Published
    Description: 175-184
    Description: 4.1. Metodologie sismologiche per l'ingegneria sismica
    Description: JCR Journal
    Description: open
    Keywords: site effects ; fourier analysis ; 04. Solid Earth::04.06. Seismology::04.06.01. Earthquake faults: properties and evolution
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  • 151
    Publication Date: 2017-04-04
    Description: Geochemical investigations have shown that there is a considerable inflow of gas into both crater lakes of Monticchio, Southern Italy. These lakes are located in two maars that formed 140 000 years ago during Mt. Vulture volcano s last eruptive activity. Isotopic analyses suggest that CO2 and helium are of magmatic origin; the latter displays 3He ⁄ 4He isotope ratios similar to those measured in olivines of the maar ejecta. In spite of the fact that the amount of dissolved gases in the water is less than that found in Lake Nyos (Cameroon), both the results obtained and the historical reports studied indicate that these crater lakes could be highly hazardous sites, even though they are located in a region currently considered inactive. This could be of special significance in very popular tourist areas such as the Monticchio lakes, which are visited by about 30 000 people throughout the summer, for the most part on Sundays.
    Description: Published
    Description: 83-87
    Description: 2.4. TTC - Laboratori di geochimica dei fluidi
    Description: JCR Journal
    Description: reserved
    Keywords: volcanic gases ; gas hazard ; crater lakes ; 04. Solid Earth::04.04. Geology::04.04.12. Fluid Geochemistry ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk
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  • 152
    Publication Date: 2017-04-04
    Description: On 2009 April 6, the Central Apennines were hit by an Mw = 6.3 earthquake. The region had been shaken since 2008 October by seismic activity that culminated in two foreshocks with Mw 〉 4, 1 week and a few hours before the main shock. We computed seismic moment tensors for 26 events with Mw between 3.9 and 6.3, using the Regional Centroid Moment Tensor (RCMT) scheme. Most of these source parameters have been computed within 1 hr after the earthquake and rapidly revised successively. The focal mechanisms are all extensional, with a variable and sometimes significant strike-slip component. This geometry agrees with the NE–SW extensional deformation of the Apennines, known from previous seismic and geodetic observations. Events group into three clusters. Those located in the southern area have larger centroid depths and a wider distribution of T-axis directions. These differences suggest that towards south a different fault systemwas activated with respect to the SW-dipping normal faults beneath L’Aquila and more to the north.
    Description: In press
    Description: 1.1. TTC - Monitoraggio sismico del territorio nazionale
    Description: JCR Journal
    Description: open
    Keywords: moment tensor ; seismotectonics ; L'Aquila ; 04. Solid Earth::04.07. Tectonophysics::04.07.04. Plate boundaries, motion, and tectonics
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  • 153
    Publication Date: 2017-04-04
    Description: The strong motion data of 2009 April 6 L’Aquila (Central Italy) earthquake (Mw = 6.3) and of 12 aftershocks (4.1 ≤ Mw ≤ 5.6) recorded by 56 stations of the Italian strong motion network are spectrally analysed to estimate the source parameters, the seismic attenuation, and the site amplification effects. The obtained source spectra for S wave have stress drop values ranging from 2.4 to 16.8 MPa, being the stress drop of the main shock equal to 9.2 MPa. The spectral curves describing the attenuation with distance show the presence of shoulders and bumps, mainly around 50 and 150 km, as consequence of significant reflected and refracted arrivals from crustal interfaces. The attenuation in the first 50 km is well described by a quality factor equal to Q( f ) = 59 f 0.56 obtained by fixing the geometrical spreading exponent to 1. Finally, the horizontal-to-vertical spectral ratio provides unreliable estimates of local site effects for those stations showing large amplifications over the vertical component of motion.
    Description: Published
    Description: 1573–1579
    Description: 4.1. Metodologie sismologiche per l'ingegneria sismica
    Description: JCR Journal
    Description: open
    Keywords: Generalized inversion ; strong-motion ; 04. Solid Earth::04.06. Seismology::04.06.04. Ground motion
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 154
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 801-818 
    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.
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  • 155
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 827-830 
    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.
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  • 156
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 835-837 
    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.
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  • 157
    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.
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  • 158
    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.
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  • 159
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 889-894 
    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.
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  • 160
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 857-877 
    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.
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  • 161
    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.
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  • 162
    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.
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  • 163
    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.
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  • 164
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 217-224 
    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
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  • 165
    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.
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  • 166
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 287-297 
    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.
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  • 167
    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.
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  • 168
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 323-330 
    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.
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  • 169
    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.
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  • 170
    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.
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  • 171
    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.
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  • 172
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 929-932 
    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.
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  • 173
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 939-941 
    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.
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  • 174
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 959-969 
    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.
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  • 175
    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.
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  • 176
    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.
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  • 177
    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.
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  • 178
    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.
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  • 179
    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.
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  • 180
    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.
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  • 181
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 195-203 
    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.
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  • 182
    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.
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  • 183
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 229-239 
    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.
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  • 184
    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).
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  • 185
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 253-264 
    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.
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  • 186
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 281-285 
    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
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  • 187
    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.
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  • 188
    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).
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  • 189
    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.
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  • 190
    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.
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  • 191
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 831-834 
    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.
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  • 192
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 839-842 
    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.
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  • 193
    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.
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  • 194
    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)].
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  • 195
    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.
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  • 196
    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.
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  • 197
    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.
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  • 198
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 993-1000 
    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.
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  • 199
    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.
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  • 200
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 29-32 
    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.
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