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  • Inorganic Chemistry  (83,671)
  • LUNAR AND PLANETARY EXPLORATION  (14,409)
  • Meteorology
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  • 1
    Publication Date: 2022-12-12
    Description: Isentropic analysis in this country originated with a particular purpose in view, namely as a means of using moisture distribution to determine flow patterns in the atmosphere It revealed, very successfully, certain theoretically anticipated patterns. Subsequently it has come into general use in connection with upper-air analysis but for the most part its application is dominated by the original particular purpose. A rather different approach is to use isentropic analysis in a more purely descriptive fashion as the principal tool for upper-air analysis. This demands that an isentropic chart represent synoptically as much useful information as possible and that all phases of its preparation receive due care.
    Keywords: Upper air temperature ; Meteorology
    Repository Name: Woods Hole Open Access Server
    Type: Technical Report
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  • 2
    Publication Date: 2022-06-02
    Description: This work refers to an interdisciplinary study on the archaeological site of Pyrgi, an Etruscan harbour still under excavation, located on the Lazio’s coast in Santa Severa, in the province of Rome. The objective of the research is to assess the main cause of the floods and the time the water stays in the site to determine if the floods are periodic phenomena over time or random events for guarantee a correct conservation of the site . The study is based on the combined use of geomatic technologies, meteorological and climatic models, and hydrogeological knowledge.
    Keywords: Geomatic ; Hydrogeology ; Meteorology ; Coastal Cultural Heritage ; Pyrgi
    Language: English
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  • 3
    Publication Date: 2022-02-10
    Description: Abstract
    Description: Integrated water vapor above Iquique airport from March 2018 to March 2019 measured with Microwave radiometer HATPRO-FOGHAT. Retrieval is based on 20 Years of Radiosonde Data from Antofagasta. Radiosonde data has been preprocessed with a relative humidity threshold of 90% for cloud formation.
    Keywords: Climatology/Meteorology/Atmosphere ; Meteorology ; Remote Sensing ; Integrated water vapor (IWV)
    Type: Dataset , Dataset
    Format: NetCDF
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  • 4
    Publication Date: 2022-02-10
    Description: Abstract
    Description: Liquid water path above Iquique airport from March 2018 to March 2019 measured with Microwave radiometer HATPRO-FOGHAT. Retrieval is based on 20 Years of Radiosonde Data from Antofagasta. Radiosonde data has been preprocessed with a relative humidity threshold of 80% for cloud formation.
    Keywords: Climatology/Meteorology/Atmosphere ; Meteorology ; Remote Sensing ; Cloud liquid water path (LWP)
    Type: Dataset , Dataset
    Format: NetCDF
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  • 5
    Publication Date: 2022-02-10
    Description: Abstract
    Description: Liquid water path above Iquique airport from March 2018 to March 2019 measured with Microwave radiometer HATPRO-FOGHAT. Retrieval is based on 20 Years of Radiosonde Data from Antofagasta. Radiosonde data has been preprocessed with a relative humidity threshold of 85% for cloud formation.
    Keywords: Climatology/Meteorology/Atmosphere ; Meteorology ; Remote Sensing ; Cloud liquid water path (LWP)
    Type: Dataset , Dataset
    Format: NetCDF
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  • 6
    Publication Date: 2022-02-10
    Description: Abstract
    Description: Integrated water vapor above Iquique airport from March 2018 to March 2019 measured with Microwave radiometer HATPRO-FOGHAT. Retrieval is based on 20 Years of Radiosonde Data from Antofagasta. Radiosonde data has been preprocessed with a relative humidity threshold of 95% for cloud formation.
    Keywords: Climatology/Meteorology/Atmosphere ; Meteorology ; Remote Sensing ; Integrated water vapor (IWV)
    Type: Dataset , Dataset
    Format: NetCDF
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  • 7
    Publication Date: 2022-02-10
    Description: Abstract
    Description: Liquid water path above Iquique airport from March 2018 to March 2019 measured with Microwave radiometer HATPRO-FOGHAT. Retrieval is based on 20 Years of Radiosonde Data from Antofagasta. Radiosonde data has been preprocessed with a relative humidity threshold of 90% for cloud formation.
    Keywords: Climatology/Meteorology/Atmosphere ; Meteorology ; Remote Sensing ; Cloud liquid water path (LWP)
    Type: Dataset , Dataset
    Format: NetCDF
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  • 8
    Publication Date: 2022-02-10
    Description: Abstract
    Description: Liquid water path above Iquique airport from March 2018 to March 2019 measured with Microwave radiometer HATPRO-FOGHAT. Retrieval is based on 20 Years of Radiosonde Data from Antofagasta. Radiosonde data has been preprocessed with a relative humidity threshold of 95% for cloud formation.
    Keywords: Climatology/Meteorology/Atmosphere ; Meteorology ; Remote Sensing ; Cloud liquid water path (LWP)
    Type: Dataset , Dataset
    Format: NetCDF
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  • 9
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    Frontiers Media SA
    Publication Date: 2024-04-04
    Description: The Frontiers in Chemistry Editorial Office team are delighted to present the inaugural “Frontiers in Chemistry: Rising Stars” article collection, showcasing the high-quality work of internationally recognized researchers in the early stages of their independent careers. All Rising Star researchers featured within this collection were individually nominated by the Journal’s Chief Editors in recognition of their potential to influence the future directions in their respective fields. The work presented here highlights the diversity of research performed across the entire breadth of the chemical sciences, and presents advances in theory, experiment and methodology with applications to compelling problems. This Editorial features the corresponding author(s) of each paper published within this important collection, ordered by section alphabetically, highlighting them as the great researchers of the future. The Frontiers in Chemistry Editorial Office team would like to thank each researcher who contributed their work to this collection. We would also like to personally thank our Chief Editors for their exemplary leadership of this article collection; their strong support and passion for this important, community-driven collection has ensured its success and global impact.
    Keywords: Green and Sustainable Chemistry ; Analytical Chemistry ; Theoretical and Computational Chemistry ; Polymer Chemistry ; Medicinal and Pharmaceutical Chemistry ; Organic Chemistry ; Nanoscience ; Catalysis and Photocatalysis ; Supramolecular Chemistry ; Electrochemistry ; Inorganic Chemistry ; Chemical Biology ; thema EDItEUR::P Mathematics and Science::PD Science: general issues
    Language: English
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  • 10
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    Frontiers Media SA
    Publication Date: 2024-04-04
    Description: This eBook is a collection of articles from a Frontiers Research Topic. Frontiers Research Topics are very popular trademarks of the Frontiers Journals Series: they are collections of at least ten articles, all centered on a particular subject. With their unique mix of varied contributions from Original Research to Review Articles, Frontiers Research Topics unify the most influential researchers, the latest key findings and historical advances in a hot research area! Find out more on how to host your own Frontiers Research Topic or contribute to one as an author by contacting the Frontiers Editorial Office: frontiersin.org/about/contact
    Keywords: parameter estimation ; superior collicullus ; Electroencephalography ; Ostrinia furnacalis ; excitable media ; Avian song system ; Meteorology ; thema EDItEUR::P Mathematics and Science::PD Science: general issues
    Language: English
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  • 11
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    Springer Nature | Palgrave Macmillan
    Publication Date: 2024-04-04
    Description: Climate Change; Climate Forecasting; Energy Industry; Climate Risk Management; Meteorology
    Keywords: Climate Change ; Climate Forecasting ; Energy Industry ; Climate Risk Management ; Meteorology ; bic Book Industry Communication::P Mathematics & science::PH Physics ; thema EDItEUR::P Mathematics and Science::PH Physics
    Language: English
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  • 12
    Publication Date: 2023-06-16
    Description: Global navigation satellite system (GNSS) remote sensing of the troposphere, called GNSS meteorology, is already a well-established tool in post-processing applications. Real-time GNSS meteorology has been possible since 2013, when the International GNSS Service (IGS) established its real-time service. The reported accuracy of the real-time zenith total delay (ZTD) has not improved significantly over time and usually remains at the level of 5–18 mm, depending on the station and test period studied. Millimeter-level improvements are noticed due to GPS ambiguity resolution, gradient estimation, or multi-GNSS processing. However, neither are these achievements combined in a single processing strategy, nor is the impact of other processing parameters on ZTD accuracy analyzed. Therefore, we discuss these shortcomings in detail and present a comprehensive analysis of the sensitivity of real-time ZTD on processing parameters. First, we identify a so-called common strategy, which combines processing parameters that are identified to be the most popular among published papers on the topic. We question the popular elevation-dependent weighting function and introduce an alternative one. We investigate the impact of selected processing parameters, i.e., PPP functional model, GNSS selection and combination, inter-system weighting, elevation-dependent weighting function, and gradient estimation. We define an advanced strategy dedicated to real-time GNSS meteorology, which is superior to the common one. The a posteriori error of estimated ZTD is reduced by 41%. The accuracy of ZTD estimates with the proposed strategy is improved by 17% with respect to the IGS final products and varies over stations from 5.4 to 10.1 mm. Finally, we confirm the latitude dependency of ZTD accuracy, but also detect its seasonality.
    Description: H2020 Marie Skłodowska-Curie Actions http://dx.doi.org/10.13039/100010665
    Keywords: ddc:526 ; GNSS ; Meteorology ; Real time ; ZTD
    Language: English
    Type: doc-type:article
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  • 13
    Publication Date: 2022-02-25
    Description: Abstract
    Description: Classification of the state of the atmospheric boundary layer at Diego Aracena Aitport, Iquique, Chile. Profiles of vertical and horizontal wind speed and backscatter coefficient (measured with a Doppler Wind Lidar) as well as thermal stratification at the surface (Thermo-Hygrometers at ~1m and ~2m height) are used to identify height regions without and with turbulence, clouds and precipitation . In a second step the sources of this turbulence are identified (clouds, surface heating or wind shear). For details of the method see Manninen, A., T. Marke, E. O'Connor, and M. Tuononen, 2018: Atmospheric boundary layer classification with Doppler lidar, J. Geophys. Res. , 123, DOI:10.1029/2017JD028169. For daily plots see: http://tiny.cc/iqq_cn_bl_class
    Keywords: Climatology/Meteorology/Atmosphere ; Meteorology ; Remote Sensing ; LiDAR ; Stratocumulus ; Wind ; Clouds
    Type: Dataset , Dataset
    Format: NetCDF
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  • 14
    Publication Date: 2022-02-10
    Description: Abstract
    Description: Wind profiles from March 2018 - MArch 2019 from Doppler Wind Lidar installed at Iquique airport.Wind speed and direction were derived from the VAD-24 scans performed every 15minutes. Error estimates (variables delta_* in the netcdf files) are based on turbulence from vertical stare measurements.
    Keywords: Climatology/Meteorology/Atmosphere ; Meteorology ; Remote Sensing ; LiDAR ; Wind speed ; Wind direction
    Type: Dataset , Dataset
    Format: NetCDF
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  • 15
    Publication Date: 2022-05-25
    Description: During cruise 102 of the R/V Atlantis-II in the Joint Air-Sea Interaction Project (JASIN), surface meteorological data were gathered by Woods Hole Oceanographic Institution personnel from two moored buoys and from the ship. One buoy (JASIN W2/WHOI 651) carried a Vector Averaging Wind Recorder (VAWR) and a Vector Measuring Wind Recorder (VMWR); these instruments provided 18 days of intercomparison data and 38 days of meteorological data from 30 July to 6 September 1978. The other buoy (JASIN H2) carried a VMWR and gave 25 total days of data from 16 July to 10 August, and from 26 August to 1 September. A PET computer, hardwired to sensors positioned on the ship, displayed data that were logged during both legs of the cruise. Manual data were gathered by the science watches. This report describes the PET system, and displays and compares all the data. VAWR hourly meteorological data are listed for the 38 day period. Scientific interpretation of these data, such as calculations of heat fluxes, will be published separately.
    Description: Prepared for the National Science Foundation under Grants OCE77-25803 and OCE76-80174, and for the Office of Naval Research under Contract N00014-76-C-0197; NR 083-400 to the Woods Hole Oceanographic Institution.
    Keywords: Joint Air-Sea Interaction Project ; Meteorology ; Ocean-atmosphere interaction ; Atlantis II (Ship : 1963-) Cruise AII102
    Repository Name: Woods Hole Open Access Server
    Type: Technical Report
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  • 16
    Publication Date: 2022-05-26
    Description: Includes Errata
    Description: Time-series of monthly averages of latent, sensible and radiational heat fluxes and momentum fluxes at the surfaces of the North and South Atlantic Oceans were calculated from ship weather observations. These fluxes, together with values of meteorological variables have been averaged over entire Marsden squares (10X10° squares) for all months from January 1948 through December 1972. The method of computing fluxes from ship weather observations, listing of variables averaged, addition of sea-ice coverage of sub-polar regions, correction of albedos for the presence of sea ice, correction of infrared radiational exchange for humidity conditions of the upper atmosphere, and format of the data on magnetic tapes are described. Statistics of the fluxes and variables have been computed. Standard data tapes containing these time series and statistics are available.
    Description: Prepared for Climate Dynamics Research Program~ Division of Atmospheric Sciences, National Science Foundation under Grant ATM 77-01475 A01.
    Keywords: Meteorology ; Climatology
    Repository Name: Woods Hole Open Access Server
    Type: Technical Report
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  • 17
    Publication Date: 2022-05-26
    Description: The Northwest Tropical Atlantic Station (NTAS) was established to address the need for accurate air-sea flux estimates and upper ocean measurements in a region with strong sea surface temperature anomalies and the likelihood of significant local air–sea interaction on inter-annual to decadal timescales. The approach is to maintain a surface mooring outfitted for meteorological and oceanographic measurements at a site near 15N, 51W by successive mooring turnarounds. These observations are used to investigate air–sea interaction processes related to climate variability. The NTAS Ocean Reference Station (ORS NTAS) is supported by the National Oceanic and Atmospheric Administration’s (NOAA) Ocean Observing and Monitoring Division. This report documents recovery of the NTAS-15 mooring and deployment of the NTAS-16 mooring. Both moorings used Surlyn foam buoys as the surface element. These buoys were outfitted with two Air–Sea Interaction Meteorology (ASIMET) systems. Each system measures, records, and transmits via Argos satellite the surface meteorological variables necessary to compute air–sea fluxes of heat, moisture and momentum. The upper 160 m of the mooring line were outfitted with oceanographic sensors for the measurement of temperature, salinity and velocity. The mooring turnaround was done by the Upper Ocean Processes Group of the Woods Hole Oceanographic Institution (WHOI), onboard R/V Endeavor (cruise EN590). The cruise took place between January 21 and February 8 2017. The NTAS-16 mooring was deployed on January 30, and the NTAS-15 mooring was recovered on January 31. A 24-hour intercomparison period was conducted on January 29 in front of the NTAS 15 buoy, and again on February 1 in front of the NTAS 16 buoy. During the inter-comparisons, data from instrumentation on the buoys, telemetered through Argos satellite system, and the ship’s meteorological and oceanographic measurements were monitored while the ship was stationed 0.2 nm downwind of the buoys. This report describes these operations, as well as other work done on the cruise and some of the pre-cruise buoy preparations. Other operations during EN590 consisted in the recovery and deployment of the Meridional Overturning Variability Experiment (MOVE) Pressure Inverted Echo Sounders (PIES) at two MOVE arrays (MOVE 1 in the east, and MOVE 3 in the west near Guadeloupe). Acoustic downloads of data from (PIES) and subsurface mooring (MOVE1, 3 and 4) were also conducted. MOVE is designed to monitor the integrated deep meridional flow in the tropical North Atlantic.
    Description: Funding was provided by the National Oceanic and Atmospheric Administration under Grant No. NA14OAR4320158.
    Keywords: Hydrography ; Oceanographic instruments ; Meteorology ; Endeavor (Ship: 1976-) Cruise EN590
    Repository Name: Woods Hole Open Access Server
    Type: Technical Report
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  • 18
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2017-02-10
    Description: Author: Jake Yeston
    Keywords: Inorganic Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 19
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2017-01-27
    Description: Author: Jake Yeston
    Keywords: Inorganic Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 20
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2017-01-27
    Description: Polynitrogens have the potential for ultrahigh-performing explosives or propellants because singly or doubly bonded polynitrogens can decompose to triply bonded dinitrogen (N2) with an extraordinarily large energy release. The large energy content and relatively low activation energy toward decomposition makes the synthesis of a stable polynitrogen allotrope an extraordinary challenge. Many elements exist in different forms (allotropes)—for example, carbon can exist as graphite, diamond, buckyballs, or graphene. However, no stable neutral allotropes are known for nitrogen, and only two stable homonuclear polynitrogen ions had been isolated until now—namely, the N3− anion (1) and the N5+ cation (2). On page 374 of this issue, Zhang et al. (3) report the synthesis and characterization of the first stable salt of the cyclo-N5− anion, only the third stable homonuclear polynitrogen ion ever isolated. Author: Karl O. Christe
    Keywords: Inorganic Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 21
    Publication Date: 2021-05-19
    Description: Basic data concerning the sources of coastal marine pollution of both urban and industrial origin in Tunisia are presented as well as basic information regarding the relationship between marine pollution and oceanography, topography and hydrology and human activity. This study will serve as a basis for more precise measurements of degrees of pollution and for monitoring the coastal marine pollution in Tunisia.
    Description: Dans ce travail ont été rassemblées les données de base concernant les sources de pollution marine côtière en Tunisie, pollution d'origines urbaine et industrielle, ainsi que les informations de base relatives, d’une part, à l’océanographie, la topographie et l’hydrologie et, d’autre part, aux activités humaines en relation avec la pollution du milieu marin. Ce travail constitue un inventaire a priori des sources de pollution et servira de base à des mesures précises des degrés de pollution et de surveillance de la pollution marine côtière en Tunisie.
    Description: Published
    Keywords: Meteorology ; Oceanology ; Sea water ; Pollutants ; Pollution effects ; Marine
    Repository Name: AquaDocs
    Type: Journal Contribution , Refereed
    Format: pp 53-95
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  • 22
    Publication Date: 2022-05-26
    Description: Meteorological data have been gathered from a moored surface buoy at 34°N, 70°W in the Long Term Upper Ocean Study (LOTUS) experiment. The meteorological results from the first year of LOTUS are encouraging; the data returned from redundant sensors agree closely. Surface heat fluxes calculated from the observations show the annual cycle of heat transfer to the mixed layer. This report documents the meteorological sensors on the LOTUs-3 (May 1982-october 1982) and LOTUS-4 (November 1982-March 1983) surface buoys. It describes in detail the telemetry of the meteorological data via the ARGOS satellite system. The measurements returned from LOTUS-3 are presented and evaluated. Monthly heat fluxes at the sea surface are computed using the bulk formulas and compared with the long-term means. The errors in the heat fluxes have been estimated.
    Description: Prepared for the Office of Naval Research under Contract N00014-76-C-0197; NR 083-400.
    Keywords: Meteorology ; Oceanus (Ship : 1975-) Cruise OC119 ; Oceanus (Ship : 1975-) Cruise OC129 ; Endeavor (Ship: 1976-) Cruise EN97
    Repository Name: Woods Hole Open Access Server
    Type: Technical Report
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  • 23
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-04-15
    Description: The United States has fallen behind Europe in adopting a modern weather balloon system. Twice a day, hundreds of hydrogen- or helium-filled balloons lift off from stations around the world, carrying temperature, pressure, and humidity sensors that provide crucial information for weather forecast models. But for more than three-quarters of the world's 800 balloon stations, the information is streamed in an antiquated alphanumeric format; these stations have failed to meet a 2014 deadline to upgrade to a new, more powerful binary format. Moreover, many forecasters who use balloon data have also failed to switch over, and are now facing data gaps as nations turn off the old, alphanumeric streams. The U.S. Global Forecast System, for example, does not incorporate the new, binary data. Author: Eric Hand
    Keywords: Meteorology
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 24
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-09-09
    Description: Author: Jake Yeston
    Keywords: Inorganic Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 25
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    American Association for the Advancement of Science (AAAS)
    In: Science
    Publication Date: 2016-11-11
    Description: Author: Jake Yeston
    Keywords: Inorganic Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 26
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    Woods Hole Oceanographic Institution
    Publication Date: 2022-05-26
    Description: This report presents meteorological data recorded by the MR on the three deployments of Tropic Heat moorings, within 1.5 degrees north and south of the equator at approximately 134°W and 140°W. Parameters recorded included vector averaged wind speed and direction, air and sea temperatures, insolation, barometric pressure, and relative humidity although not all parameters were recorded on all deployments . The deployments were all nominally six months . Data recovery was poor because of instrument and mooring failures.
    Description: Funding was provided by the National Science Foundation under grant Number OCE 83-1 0982.
    Keywords: Buoys ; Meteorology
    Repository Name: Woods Hole Open Access Server
    Type: Technical Report
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  • 27
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    Woods Hole Oceanographic Institution
    Publication Date: 2022-05-26
    Description: This report presents meteorological data from three deployments of SEQUAL moorings SS and S6 (nominal positions 0°N, 24°W and 0°N, 15°W) and also from a post SEQUAL deployment at SEQUAL mooring site S2 at 0°N, 28°W. Parameters recorded include vector averaged wind speed and direction, air and sea surface temperatures, insolation, barometric pressure and relative humidity although not all parameters were recorded on all deployments. All deployments were nominally six months.
    Description: Funding was provided by the National Science Foundation under grant Numbers OCE 81-22061 and OCE 82-111 08.
    Keywords: Meteorology ; Buoys
    Repository Name: Woods Hole Open Access Server
    Type: Technical Report
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  • 28
    Publication Date: 2015-09-19
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Ostrander, Chris E -- Lautenbacher, Conrad C -- England -- Nature. 2015 Sep 17;525(7569):321. doi: 10.1038/525321d.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉University of Hawaii at Manoa, Honolulu, Hawaii, USA. ; GeoOptics, Dunwoody, Georgia, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/26381978" target="_blank"〉PubMed〈/a〉
    Keywords: *International Cooperation ; Meteorology ; Oceanography/*standards ; *Oceans and Seas ; Pacific Islands ; Pacific Ocean ; United States
    Print ISSN: 0028-0836
    Electronic ISSN: 1476-4687
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
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  • 29
    Publication Date: 2021-05-19
    Description: Published
    Description: Mécanismes hydologiques
    Description: Climat
    Keywords: Meteorology ; Hydrology
    Repository Name: AquaDocs
    Type: Journal Contribution , Non-Refereed , Article
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  • 30
    Publication Date: 2021-05-19
    Description: Continuous measurements were taken of oceanographic and meteorological parameters for two stations of the Global Ocean Observing System of the Southwest Caribbean, framed in the INAP project. The response of the surface layer, to atmospheric events, allowed to differentiate the pass of two cold fronts by Johnny Cay station (San Andres Island) and the arrival of the “Veranillo” in the sensors of Tesoro Island (Islas del Rosario, Cartagena). The cold fronts produced a decrease in the atmospheric pressure, air temperature, caused radical changes in wind direction and speed followed by precipitation. This situation lowered the sea surface temperature, the surface layer pH and rose momentarily the sea level. The “Veranillo” came to Archipelago of Rosario generating a strong increase in wind speed and solar radiation. The response in the sea surface layer was evident through a significant increase in sea level.
    Description: INVEMAR
    Description: Published
    Description: Veranillo; INAP
    Keywords: Meteorology ; Oceanography ; Cold fronts
    Repository Name: AquaDocs
    Type: Journal Contribution , Refereed , Article
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  • 31
    Publication Date: 2021-01-30
    Description: Observing System and the WMO Information System (EC-WG/WIGOS-WIS-4) was held at the WMO Secretariat in Geneva, Switzerland, from 10 to 11 February 2011. The session was chaired by Prof A. D. Moura (Brazil), Third Vice-President of WMO. EC-WG/WIGOS-WIS reviewed and endorsed the following WIGOS documents to be submitted to the sixteenth Congress (Cg-XVI): (a) Report on the Integration between the WMO Observing Systems (Appendix II); (b) WIGOS Test of Concept Development and Implementation Plan (WDIP) (Appendix III); (c) WIGOS Concept of Operations (CONOPS) (Appendix IV); (d) WIGOS Development and Implementation Strategy (WDIS) (Appendix V). Furthermore, EC-WG/WIGOS-WIS-4 formulated its recommendations on the WIGOS implementation in the form of Draft Resolution 11.3/1 (Cg-XVI) – Implementation of the WMO Integrated Global Observing System (WIGOS) (Appendix VII). When discussing the individual Agenda Items, particular attention was given to pre-Congress actions, on the enhancement of communication on WIGOS matters.
    Description: Supported by World Meteorological Organization.
    Description: Document available in English.
    Description: Published
    Keywords: Meteorology ; Marine meteorology
    Repository Name: AquaDocs
    Type: Report , Non-Refereed
    Format: 92
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  • 32
    Publication Date: 2021-01-30
    Description: The second session of the Executive Council Working Group on the WMO Integrated Global Observing System and the WMO Information System (EC-WG/WIGOS-WIS) was held at the WMO Secretariat in Geneva, Switzerland, from 6 to 8 May 2009, and was chaired by Prof A. Divino Moura (Brazil), Third Vice-President of the WMO and Chair of EC WG. EC-WG/WIGOS-WIS was briefed on major deliberations of the first session of its Subgroup on the WMO Integrated Global Observing System (SG-WIGOS-1) Geneva, Switzerland, 10 - 13 November 2008; the CBS Technical Conference on WIGOS (TECO-WIGOS) (Dubrovnik, Croatia, 23-24 March 2009); and the fourteenth session of the Commission for Basic Systems (CBS-XIV) (Dubrovnik, Croatia, 25 March - 2 April 2009). EC-WG/WIGOS-WIS was briefed on the status of: (a) Implementation of the WIS Project and its Implementation Plan; (b)nWIGOS Pilot and Demonstration Projects; (c) Review of the WIGOS Concept of Operation (CONOPS); (d) Implementation of WIGOS Development and Implementation Plan (WDIP) and its corresponding update; (e) Monitoring of the implementation of WIGOS and WIS through Rolling Requirements Review; (f) Revision of WMO Technical Regulations related to WIGOS and WIS implementation. Based on the outcomes of the consideration of the individual Agenda Items, EC-WG/WIGOS-WIS articulated its guidance, advice and recommendations regarding the further development of the implementation of WIS, WIGOS concept, coordination of WIGOS and WIS plans; it agreed on the versions of CONOPS (Appendix II) and WDIP (Appendix III) to be submitted to EC-LXI for consideration and endorsement.
    Description: Supported by World Meteorological Organization.
    Description: Document available in English.
    Description: Published
    Keywords: Meteorology ; UNESCO ; Marine meteorology
    Repository Name: AquaDocs
    Type: Report , Non-Refereed
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  • 33
    Publication Date: 2021-01-30
    Description: WMO/ IOC
    Description: Document available in English
    Description: Published
    Description: management
    Keywords: Meteorology ; Marine meteorology
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    Type: Report , Non-Refereed
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  • 34
    Publication Date: 2021-01-30
    Description: The first session of the Subgroup on the WMO Integrated Global Observing System (EC-WG/SG-WIGOS-1) of the Executive Council Working Group on the WMO Integrated Global Observing System (WIGOS) and the WMO Information System (WIS) was held at the WMO Secretariat in Geneva, Switzerland, from 10 to 13 November 2008, and was chaired by Dr John Nash (UK), the President of the Commission for Instruments and Methods of Observation (CIMO) and Chair of the Subgroup. Main attention of the SG-WIGOS was focused on the status of WIGOS Pilot and Demonstration Projects and their potential input for the update of WIGOS Concept of Operations (CONOPS) and WIGOS Development and Implementation Plan (WDIP); on the elaboration of the WIGOS Integration Levels; on a review of needs and potential problems of WMO co-sponsored observing systems; and update of CONOPS and WDIP. SG-WIGOS discussed a scope, time frame and role of WIGOS Pilot Projects. When doing that, guidance from Cg-XV were taken into account that Pilot Projects should be designed to test concepts, identify problem areas and to help in elaborating WDIP by inputs from respective technical commission.
    Description: Supported by World Meteorological Organization.
    Description: Document available in English.
    Description: Published
    Keywords: Meteorology ; Marine meteorology
    Repository Name: AquaDocs
    Type: Report , Non-Refereed
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  • 35
    Publication Date: 2021-05-19
    Description: The third session of the Executive Council Working Group on the WMO Integrated Global Observing System and the WMO Information System (EC-WG/WIGOS-WIS) was held at the WMO Secretariat in Geneva, Switzerland, from 24 to 26 March 2010. The session was chaired by Prof A. Divino Moura (Brazil), Third Vice-President of the WMO and Chair of EC WG. EC-WG/WIGOS-WIS reviewed major deliberations of the second session of its Subgroup on WIGOS (SG-WIGOS-2, Geneva, Switzerland, 19-23 October 2009), and the sixth session of the Inter-Commission Group on WIS (ICG-WIS, Seoul, Republic of Korea, 22-26 February 2010) and developed appropriate proposals and recommendations. EC-WG/WIGOS-WIS further considered: (a) Report on the WIGOS Projects (Status, Evaluation, Lessons Learned); (b) WIGOS Concept of Operations (CONOPS); (c) WIGOS Test of Concept Development and Implementation Plan (WDIP); (d) WIGOS Development and Implementation Strategy (WDIS); (e) Report on the integration between the WMO observing systems. Based on the outcomes of the discussion under individual Agenda Items, EC-WG/WIGOS-WIS formulated recommendations on the further development and implementation of the WIGOS concept, the implementation of WIS, and the enhanced coordination of WIS and WIGOS activities. EC WG decided to submit the updated versions of CONOPS (Appendix II), WDIP (Appendix IV) and WDIS (Appendix V) to EC-LXII for consideration and endorsement.
    Description: Supported by World Meteorological Organization.
    Description: Document available in English.
    Description: Published
    Keywords: Meteorology ; Marine meteorology
    Repository Name: AquaDocs
    Type: Report , Non-Refereed
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  • 36
    Publication Date: 2021-05-19
    Description: Un resumen de datos meteorológicos e hidrológicos para la Bahía de Santa Marta, Caribe colombiano. Se presentan datos de precipitación, temperatura y salinidad del agua superficial para la Bahía de Santa Marta, Caribe colombiano, para el periodo de noviembre 1978 a mayo 1982. Se obtienen generalizaciones de los patrones anuales incluyendo datos ya publicados (Muller, 1979). A partir de mediciones adicionales de la variación de la temperatura del agua y de la salinidad durante el día, valores preliminares de cuantos de luz, junto con datos disponibles sobre contenido y saturación de oxigeno, pH, alcalinidad, estabilidad, dirección y velocidad del viento, horas de luz, temperatura del aire y descarga del Río Manzanares, se hace una caracterización cuantitativa de las estaciones seca y húmeda que se observan en el área investigada.
    Description: Data on rainfall, water surface temperature and salinity from the Bay of Santa Marta, Colombian Caribbean, are presented for the period November 1978 to May 1982. Including data already published (Müller, 1979) generalizations of the anual patterns are obtained. Additional measurements of the variation of water temperature and salinity in the course of one day, preliminary values of light quanta, together with available data on oxygen contení and saturation, pH, alcalinity, stability, wind direction and velocity, hours of sunshine, air temperature, and water discharge of the river Manzanares permitted a quantitative characterization of the dry and rainy season which can be observed in the área of investigad on.
    Description: Published
    Description: hydrological cycle
    Keywords: Physical oceanography ; Meteorology ; Meteorology ; Physical oceanography
    Repository Name: AquaDocs
    Type: Journal Contribution
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  • 37
    Publication Date: 2021-05-19
    Description: Durante los años 1965 a 1967 se realizaron estudios micrometeorológicos en la región xerofítica de Santa Marta. Las condiciones meteorológicas durante el tiempo de las investigaciones están descritas por los datos sobre las temperaturas y las precipitaciones, por los climatogramas y por un diagrama de la economía hídrica del suelo de 1966. La temperatura promedia del año 1966 fue 27,7° C, las precipitaciones oscilaron entre 378 y 750 milímetros anuales. En el suelo hay carencia de agua durante la mayor parte del año. Los estudios micrometeorológicos se llevaron a cabo en dos sitios, uno situado en un cardonal y el otro en la región de un bosque de galería. Los cardonales y las regiones del bosque de galería forman dos extremos respecto a la economía hídrica de la vegetación. Por la capa vegetal más cerrada y las mejores condiciones edáficas y orográficas, el microclima en el bosque de galería tiene una tendencia menor a situaciones extremas que el mismo en el cardonal. Se comunican numerosos datos sobre las temperaturas y la humedad del aire, las velocidades de las brisas y la evaporación dependientes tanto de las estaciones del año como del nivel del sobre el suelo.
    Description: During the years 1965 to 1967 micrometeorological studies were conducted in the region of Santa Marta xerophytic. Weather conditions during the time of the research are described by the data on temperatures and rainfall, by climatogram and a diagram of the ground water economy of 1966. The average temperature of 1966 was 27.7 ° C, precipitation ranged between 378 and 750 millimeters per year. On the floor there is a shortage of water during most of the year. Micrometeorological studies were conducted at two sites, one located in a cardonal and the other in the region of a gallery forest. The cactus and gallery forest regions are two extremes on the water economy of vegetation. For more closed vegetation cover and the best soil conditions and terrain, the microclimate in the gallery forest has less tendency to extremes in the same cardonal. They communicate numerous data on temperatures and humidity, the speeds of the winds and evaporation dependent both seasons as on level ground.
    Description: Published
    Keywords: Meteorology ; Meteorology
    Repository Name: AquaDocs
    Type: Journal Contribution
    Format: pp.45-75
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  • 38
    Publication Date: 2022-05-26
    Description: Originally issued as Reference No. 60-33, series later renamed WHOI-
    Description: The study is based upon the concept that climatology cannot be divorced from the dynamics of weather. An attempt is made to outline the meteorological framework of this region of the tropics. The rainfall of Trinidad is then discussed within this framework. The mean annual distribution of rainfall over the island forms a basis for the discussion of monthly distributions. Seasonal variation is pointed out and related to broad scale migrations of the subtropical anticyclones and the equatorial trough. The dual rainfall maximum occurring during the wet season is, in turn, related to the synoptic scale patterns of this season. Distribution is then examined with reference to the moist layer, wind direction and speed. Diurnal distribution is treated in detail and the mechanisms giving rise to the well-defined distribution patterns are discussed. Finally some attention is paid to shower amounts and distribution. In conclusion the rainfall of the island is summarized by relating the seasonal variations to the broadscale meteorological background and the actual distribution to the local scale influences.
    Keywords: Rain and rainfall ; Meteorology
    Repository Name: Woods Hole Open Access Server
    Type: Technical Report
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  • 39
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    Nature Publishing Group (NPG)
    Publication Date: 2010-05-14
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Earle, Sylvia -- England -- Nature. 2010 May 13;465(7295):165. doi: 10.1038/465165a.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉US National Oceanic and Atmospheric Administration, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/20463723" target="_blank"〉PubMed〈/a〉
    Keywords: Animals ; Climate ; *Conservation of Natural Resources ; *Ecology ; *Ecosystem ; *Marine Biology ; Meteorology ; *Motion Pictures as Topic ; Oceans and Seas ; Population Density
    Print ISSN: 0028-0836
    Electronic ISSN: 1476-4687
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
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  • 40
    Publication Date: 2021-05-19
    Description: Published
    Description: Echo-sounder
    Keywords: Meteorology ; Meteorology ; Fishing nets
    Repository Name: AquaDocs
    Type: Report , Non-Refereed
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  • 41
    Publication Date: 2022-05-25
    Description: The 1991 Acoustic Surface Reverberation Experiment (ASREX 91) took place in November and December off the coast of British Columbia. As part of this experiment, three moorings were deployed to characterize the environmental background. The moorings consisted of a meteorological/oceanographic mooring designed to measure surface meteorology, current and temperature in the upper 120 meters, and nondirectional wave parameters and two wave moorings which were instrumented with pitch-roll buoys to characterize the directional wave spectrum. This report presents results from these three moorings. The conditions seen during the experiment were extremely rough, with wind speeds at 3.4m above the water surface reaching a maximum of 22 m/s and wave heights reaching a maximum of over 10 meters. The air-sea flux of heat was strongly cooling, and the mixed layer deepened over the course of the experiment from approximately 40 to approximately 70 meters. Spectra of the temperature showed a strong semidiurnal tidal signal associated with temperature excursions of several degrees C. The velocity signal showed strong inertial oscilations with amplitudes of 30-50 cm/s. Weaker low-frequency and semidiurnal tidal signals were also seen. The waves were very strong with significant wave heights of 5-6 meters persisting for up to 2 weeks at a time. Waves were generally out of the south or the west.
    Description: Funding was provided by the Ocean Acoustics Program (Code 324OA) of the Office of Naval Research under contract N00014-91-J-1891.
    Keywords: North Pacific ; Meteorology ; Oceanography ; Moored instrument measurements ; Thomas G. Thompson (Ship) Cruise TN4 ; Thomas G. Thompson (Ship) Cruise TN5
    Repository Name: Woods Hole Open Access Server
    Type: Technical Report
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  • 42
    Publication Date: 2022-05-26
    Description: The Third Acoustic Surface Reverberation Experiment (AS REX III) took place from December 1993 to March 1994 at Site L (34°N, 70°W) in the mid-Atlantic. As part of this experiment, two moorings were deployed to measure the environmental background. A meteorological and oceanographic mooring was deployed to characterize the surface wind stress, buoyancy flux, and the current and temperature structure over the top 500 meters. A Seatex Wavescan buoy was deployed to characterize the directional wave spectrum. This report presents results from these moorings. Wind speeds up to 25 m/s were seen, with significant heat losses (up to 1050 W/m2) when cold continental air moved out over the warm Atlantic. The wave heights ranged up to 8 m, with significant wave heights of several meters persisting for relatively long periods. Wave height and period, nondirectional spectra, directional spectra and a typology of wave events are presented and related to surface forcing.
    Description: Funding was provided by the Office of Naval Research through Grant No. NOOOl4-91-J-1891.
    Keywords: Meteorology ; Oceanography ; Moored instrument measurements ; Mid-Atlantic ; Knorr (Ship : 1970-) Cruise ; Edwin Link (Ship) Cruise
    Repository Name: Woods Hole Open Access Server
    Type: Technical Report
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  • 43
    Publication Date: 2022-05-26
    Description: An array of moorings at four sites at a mid-shelf location in the mid-Atlantic Bight was deployed for a period of 10 months beginning in August 1996 as part of the Coastal Mixing and Optics Experiment (CMO), funded by the Office of Naval Research (ONR). The purpose of this array is to gather information to help identify and understand the vertical mixing processes influencing the evolution of the stratification over the shelf. The observations from this moored array will be used to investigate changes in the stratification in response to atmospheric forcing, surface gravity wave variabilty, surface and bottom boundary layer mixing, current shear, internal waves, and advection. This report describes the primary mooring deployments carried out by the Upper Ocean Processes (UOP) Group on the R/V Oceanus, sailing out of Woods Hole during July, August, and September of 1996.
    Description: Funding was provided by the Office of Naval Research through Grant No. N00014-95-1-0339.
    Keywords: North Atlantic ; Meteorology ; Oceanography ; Moored instrument measurements ; Oceanus (Ship : 1975-) Cruise OC284 ; Coastal Mixing and Optics (CMO) Experiment
    Repository Name: Woods Hole Open Access Server
    Type: Technical Report
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  • 44
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-26
    Description: The physical processes which result in the formation of clouds and the production of precipitation have been described by numerous meteorologists. The genetical classification has been summarized by Petterssen as follows: (1) Clouds and precipitation types which form in unstable air masses, (2) Clouds and precipitation types which form in stable air masses, (3) Clouds and precipitation types which form in connection with quasi-horizontal inversions in the free atmosphere, and (4) Frontal clouds and precipitation forms. In general, the procedure adopted for the forecasting of these meteorological elements can also be subdivided into the same four categories. Since the distribution of the elements in the atmosphere is never constant with time, the problem of forecasting cloudiness and precipitation is sometimes diffcult. A detailed discussion of qualitative and quantitative prognostic methods can be found in various standard meteorological texts. However, present methods are not entirely adequate and it is the aim of this investigation to contribute to the solution of the forecast problem. This study has been divided into two main sections, viz., (1) Clouds and precipitation types which occur at frontal surfaces as the result of frontal lifting, and (2) Clouds and precipitation types which occur within air masses as the result of horizontal convergence within the wind field. (1) Frontal Surfaces. In a recent study of fronts and frontogenesis, Petterssen and Austin have investigated the processes that tend to create wind shear, or vorticity, along fronts. It was found that, in general, an increase or decrease in shear is accompanied by a change in the vertical velocity field at a front. Since cloudiness and precipitation arise from the ascending velocities at frontal surfaces, the possibility of forecasting the change in horizontal shear at a front will be investigated. Furthermore, it has been shown that the vertical velocity of either air mass at a frontal surface can be determined from the velocity of the front and the horizontal wind velocity. The wind velocities in the free atmosphere can be obtained with a reasonable degree of accuracy, but the front velocity cannot always be evaluated with the same accuracy. Because it is important to determine the magnitude or at least the sign of the vertical velocities, a kinematical study will be made of the displacement of frontal surfaces. (2) Horizontal Convergence. In 1931 Giao published an explanation of the origin of clouds and precipitation in the vicinity of moving cyclones, without introducing the concept of frontal surfaces. Giao claimed that most condensation phenomena could be attributed to the cooling produced by local pressure changes and the horizontal convergence which arises from the meridional component of the wind velocity. The conclusions are conveniently summarized by Haurwitz, together with a short discussion of Giao's theory. Since some systems of clouds and precipitation types may result solely from convergence in the horizontal flow, an attempt wil be made to evaluate this effect quantitatively.
    Keywords: Clouds ; Precipitation ; Meteorology
    Repository Name: Woods Hole Open Access Server
    Type: Book
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  • 45
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    Publication Date: 2021-01-30
    Description: The Fifth EUMETSAT User Forum in Africa was organised in Dakar, Senegal, by EUMETSAT, the World Meteorological Organization (WMO) and the Ministry of Equipment and Transport of the Republic of Senegal. The Forum was held from 30 September to 4 October 2002 with over 160 participants representing most African and European countries. Representatives of the following African Intergovernmental Regional Associations were present: Economic Community of West African States (ECOWAS), Intergovernmental Authority on Development (IGAD), Intergovernmental Oceanographic Commission of UNESCO (IOC) and Southern Africa Transport and Communications Commission (SATCC), Communauté Economique et Monétaire de l'Afrique Centrale (CEMAC), as well as representatives of the European Commission and the Food and Agriculture Organisation of the UN (FAO).
    Description: EUMETSAT
    Description: Published
    Keywords: Meteorology
    Repository Name: AquaDocs
    Type: Proceedings Paper , Non-Refereed
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  • 46
    Publication Date: 2022-05-25
    Description: To investigate vertical mixing processes influencing the evolution of the stratification over continental shelves a moored array was deployed on the New England shelf from August 1996 to June 1997 as part of the Office of Naval Research's Coastal Mixing and Optics program. The array consisted of four mid-shelf sites instrumented to measure oceanic (currents, temperature, salinity, pressure, and surface gravity wave spectra) and meteorological (winds, surface heat flux, precipitation) variables. This report presents a description of the moored array, a summary of the data processing, and statistics and time-series plots summarizing the data. A report on the mooring recovery cruise and a summary of shipboard CTD surveys taken during the mooring deployment are also included.
    Description: Funding was provided by the Office of Naval Research under Contract No. N00014-95-1-0339.
    Keywords: Meteorology ; Oceanography ; North Atlantic ; Moored instrument measurements ; Ocean-atmosphere interaction ; Oceanic mixing ; Oceanus (Ship : 1975-) Cruise OC305
    Repository Name: Woods Hole Open Access Server
    Type: Technical Report
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  • 47
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    In:  Eos Trans. AGU, Prague, Wiley, vol. 82, no. 20, pp. 222 & 225, pp. B09404, (ISSN: 1340-4202)
    Publication Date: 2001
    Keywords: Statistical investigations ; Earthquake risk ; 3344 ; Meteorology ; and ; atmospheric ; dynamics ; Paleoclimatology ; 1620 ; Global ; change ; Climate ; dynamics ; (3309) ; climate ; changes ; 6309 ; Policy ; sciences ; Decision ; making ; under ; uncertainty ; advice
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  • 48
    Electronic Resource
    Electronic Resource
    Springer
    International journal of biometeorology 44 (2000), S. 198-203 
    ISSN: 1432-1254
    Keywords: Keywords Urban heat island ; Coastal city ; Meteorology ; Aveiro (Portugal)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geography , Physics
    Notes: Abstract  This project arose from the need to study the phenomenon of the urban heat island, since only by recognising this phenomenon can we moderate it to improve the human and urban environments. Not only big cities develop urban heat islands. This study detected the presence and recorded the characteristics of an urban heat island in the small coastal city of Aveiro, Portugal. The study was developed through the scheduled measurements of air temperature and the analysis of the geographical, meteorological and urban conditions. The form and intensity of Aveiro’s heat island are a response to the interaction of three principal factors: the urban morphology (the hottest zones in the city are those with the tallest and the highest density of buildings, without green spaces and with intense generation of heat from traffic, commerce and services); the meteorological conditions (the intensity of the island is at its maximum when the sky is totally clear and there is no wind, and at its minimum in those situations when there is atmospheric instability, such as wind, cloud and precipitation); and the proximity of the coastal lagoon (which borders the city to the west and northwest and moderates seasonal temperatures. The urban heat island influences the comfort and health of its inhabitants, thus urban planning is very important in the moderation and prevention of this phenomenon.
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  • 49
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    In:  Rev. Geophys., Tokyo, Dt. Geophys. Ges., vol. 38, no. 1, pp. 117-139, pp. L06615, (ISSN: 1340-4202)
    Publication Date: 2000
    Keywords: 1812 ; Hydrology ; Drought ; 1854 ; Precipitation ; (3354) ; 3309 ; Meteorology ; and ; atmospheric ; dynamics ; Climatology ; (1620) ; 3322 ; Land/atmosphere ; interactions
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  • 50
    Electronic Resource
    Electronic Resource
    Springer
    International journal of biometeorology 41 (1998), S. 143-154 
    ISSN: 1432-1254
    Keywords: Key words Cattle Egret ; Southwest Pacific ; Migration ; Meteorology ; Satellite telemetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geography , Physics
    Notes: Abstract  The evolution of research into meteorological factors affecting the migration of the Cattle Egret (Ardeola ibis coromandus) in the southwestern Pacific region (Australia, New Zealand and the Tasman Sea) – from ground-based studies dependent on volunteer observers to a pilot satellite-tracking project – is reviewed and the results are related to the literature on bird migration. The predominant pattern is a seasonal migration from breeding colonies in southeast Queensland and northern New South Wales which takes place in stages along the east coastal plain under favourable meteorological conditions. Migration outward (southward) occurs in February through April and return to the breeding colonies occurs in October and November. Wintering destinations include Tasmania, southern Victoria and parts of New Zealand. Favourable meteorological conditions for migration southward include:moderate north to northwest airflow behind a high; light and variable winds in a high or col; and light and variable winds over New South Wales with moderate westerlies over Victoria and Tasmania. A satellite-tracking project helped to validate findings from the ground-based studies, provided additional information not otherwise obtainable, and demonstrated the potential of the technique to further clarify the relation between timing and staging of migration, and meteorology.
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  • 51
    ISSN: 0009-2940
    Keywords: Alkoxopalladium(II) ; Conformational analysis ; Hydrogen bonding ; Two-dimensional and cage structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of palladium acetate with two equivalents of di- and triethanolamines RN(CH2CH2OH)2 in the presence of a base affords the new chelate-stabilized alkoxo Pd(II) complexes [Pd(OCH2CH2N(R)CH2CH2OH)2] [R = Me (1), Et (2), n-Bu (3), benzyl (4) or CH2CH2OH (5)]. These N,O-ligated complexes are isolated in high yield as yellow, crystalline solids and are thermally stable despite the presence of several β-hydrogen atoms in the ligand system. Both complexes possess a square-planar palladium coordination geometry with the two oxygen atoms positioned mutually trans. The most notable difference in the molecular structures is that 1 forms a two dimensional network of intermolecular O-H≡O hydrogen bonds, whereas 5 forms intramolecular O-H⃛O hydrogen bonds, which cage the palladium center. In solution 1-4 exist as a diastereoisomeric mixture (a racemic enantiomeric pair SNSN, RNRN and a mesomeric form RNSN) in a 1:1 molar ratio, and this ratio is independent of temperature in nonalcoholic solvents, When complexes 1-4 are dissolved in protic solvents (e.g. MeOH) the diastereomeric excess is temperature-dependent due to an exchange process between the meso diastereoisomer and the (racemic) enantiomeric pair. Thermodynamic parameters for this process in a mixture of MeOH-toluene have been determined with NMR and show this process to be influenced by the steric nature of the alkyl substituent (R) on nitrogen. A conformational analysis based on 1H-NMR coupling constants within the N,O-chelate ring of complexes 1-4 provides details on the solution structure of the ring in both diastereoisomers.
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  • 52
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 13-22 
    ISSN: 0009-2940
    Keywords: Carbamates ; Catalysis ; Substituted nitrobenzenes ; Palladium ; Reductive carbonylation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The palladium-catalyzed reductive carbonylation of ortho and para-substituted nitrobenzenes has proven to be an attractive route for the synthesis of functionalized carbamates. For the Pd(1, 10-phenanthroline)2(triflate)2 catalyst system, the scope of the reaction has been studied. Substrates with electron-donating substituents at the para position were found to decrease the catalytic activity, most probably as a result of their relatively low oxidizing capacity. the selectivity towards the desired carbamate, however, was increased for these substrates. Under the influence of electron-withdrawing substituents the azoxybenzene and azobenzene derivatives became important side products. Introduction of large steric hindrance at the ortho position of the nitro substrates gave rise to an interesting side reaction, viz. methoxylation of the aromatic ring. The methoxylation reaction appeared to occur on an intermediate species in the catalytic cycle. Several functionalities have shown to be resistant to the reaction conditions required for the conversion ot the nitro group. Especially with 4-nitrobenzoic acid, an extremely high activity and selectivity was found, thus yielding a very convenient synthesis for N-protected amines containing carboxylic acid function.
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  • 53
    ISSN: 0009-2940
    Keywords: Isothiazole complexes ; Dinuclear silver(I) complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of isothiazole-based potential ligands bearing substituents with additional donor sites in the 5-position of the heterocycle was synthesized [3-Me-5-R-C3HNS; R = CH=N(CH2)2py (1), CH=NCH2py (2), CH2N(CH2CH2NEt2)2 (4), (CH2)2SMe (5)]. Upon reaction with AgO3SCF3 they formed complexes [(1)AgOSO2CF3]2 (6), [(2)AgOSO2CF3]2 (7), [(4)Ag]2+2(O3SCF-3)2 (8) and [(5)AgOSO2CF3]2 (9), respectively. 6, 8 and 9 were shown by X-ray structural analyses to consist of dimeric units L2Ag2+2, either discrete (8), coordinated by terminal CF3SO-3 units (6). In 8 and 9 the isothiazole moiety is bonded to the metal center via the ring-N. The coordination potential of the isothiazole heterocycle is discussed.
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  • 54
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 115-118 
    ISSN: 0009-2940
    Keywords: Gold complexes ; Bromonium complex ; Halogenonium complex ; Halogen, two-coordinate ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of (R3P)AuX (X = Cl, Br, I) with [(R3P)Au]+ BF-4 obtained from (R3P)AuCl and AgBF4 in tetrahydrofuran, lead to cationic binuclear gold(I) complexes of the general formula ([(R3P)Au]2X}+ BF-4. A number of chloro- (R = Ph, o-Tol, Mes, Bzl, Et), bromo- (R = Ph, o-Tol, Mes) and iodo-bridged (R = Ph, Mes) complexes of this type have been isolated and identified on the basis of their analytical and spectroscopic data. The crystal structure of bis[(triphenylphosphane)gold(I)]bromonium tetrafluoroborate was determined by single-crystal X-ray diffraction. The cations contain two-coordinate bromine atoms with an Au-Br-Au angle of 96.83(3)°.
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  • 55
    ISSN: 0009-2940
    Keywords: Arene complexes ; Ruthenium compounds ; Electrophilic substitution ; Lithiation ; Catalysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chiral or achiral (arene)(COD)Ru complexes can be made by replacing the η6-ligands of (η4-1,5-COD)(η6-1,3,5-cyclooctatriene)Ru (1) or (η4-1,5-COD)(η6-naphthalene)Ru (2) by a suitable arene. This well known reaction has been extended to mono- and dibromoarenes and we report a novel route to substituted (arene)(COD)Ru species, utilizing (bromoarene)-(COD)Ru as starting materials. These facilitate a rapid bromine-lithium exchange reaction with nBuLi at low temperatures and the lithiated species react readily with alkyl chloroformates as electrophiles. By using chiral electrophiles [alkyl = (-)-menthyl] enantiomerically pure or diastereomeric complexes containing CO2R* groups are formed, depending on the symmetry of the original complex. A diastereomeric 1:1 mixture was separated by recrystallization. All (arene)-(COD)Ru complexes tested so far are useful as catalysts for the hydrogenation of simple alkenes at room temperature.
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  • 56
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 145-154 
    ISSN: 0009-2940
    Keywords: Fluorocarbons ; C-F bond activation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The main reaction pathways which lead to the breaking of C-F bonds in perfluoroalkanes and -arenes are discussed. Emphasis is placed on recent developments and on the mechanistic patterns that emerge.
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  • 57
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The metal-vapor reactions of Co atoms with 1,3-tBu2CpH (1a), 1,3-tBu2CpH (1a), 1,2,4-tBu3CpH (1b) and EtMe4CpH (1c) are described. With 1a the two mononuclear complexes [(η5-tBu2Cp) (η4-tBu2-1,3-cyclopentadiene)Co] (2a) and [(η5-tBu2Cp)2Co] (3a) were isolated, together with the dinuclear cobalt cluster [{(η5-tBu2Cp)Co}2H3] (4a) and trace amounts of the tetranuclear cluster [{(η5-tBu2Cp)CoH}4] (5a). The molecular structures of 3a and 4a were determined by X-ray diffraction. Reaction of 1b with Co atoms afforded a single product, the dinuclear cluster [{(η5-tBu3Cp)Co}2H3] (4b), whose molecular structure was determined by single-crystal X-ray diffraction. Both, 4a and 4b exhibit extremely short Co-Co distances [2.244(1) (4a) and 2.242(1) Å (4b)], as found for the Me5Cp analog [{(η5-Me5Cp)Co}2H3] (4c). Reaction of an isomeric mixture of Me4EtCpH (1c) with Co atoms furnished the mononuclear sandwich [ (η5-Me4EtCp)(η4-Me4Et-1,3- cyclopentadiene)Co] (2b), the trinuclear hydridocobalt cluster [{(η5-Me4EtCp)Co}3H4] (6a) and the tetranuclear hydridocobalt cluster [{(η5-Me4EtCp)Co}4H4] (5c). The molecular structure of 5c was determined by X-ray crystallography and revealed a tetrahedral arrangement of the cobalt atoms. The electrochemical behavior of the dinuclear complexes 4a-4c was studied by cyclic voltammetry. Reversible redox couples were found for all three compounds, with a correlation between the degree of alkyl substitution and their respective cathodic shifts. Compounds 4a and 4b react with CO to yield the mononuclear and dinuclear complexes [ (η5- CpR)Co(CO)2] (R=1,3-tBu2, 1,2,4-tBu3) (7a and 7b) as well as [{(η5-CpR)CO}2(CO)2] (8a and 8b). Reaction of the trinuclear hydridocobalt cluster 6a and its Me5Cp analog 6b with AgBF4 in the presence of PEt3 yielded the heteronuclear clusters [{η5-Me4CPR)Co}3AgP(Et)3H4]+[BF4]- (R=Et, Me) (9a and 9b). 9a was structurally characterized by X-ray crystallography.
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  • 58
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 45-48 
    ISSN: 0009-2940
    Keywords: Metallated methyl isopropenyl ether ; Tetrahydrofurans ; 1-Oxabicyclo[4.3.0]heptanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methyl isopropenyl ether (1) has been metallated at low temperature with a 1:1 molar mixture of n-BuLi/t-BuOK in THF-hexane, and subsequently functionalized with a variety of electrophilic reagents. At temperatures higher than - 30°C, the metallated methyl isopropenyl ether (2) decomposes with formation of allene. When the suspension of 2 is allowed to warm up to room temperature in the presence of an additional equivalent of n-BuLi, the intermediary allene is converted into 1-propynyllithium (2c), which reacts with propylthiocyanate to give 1-propylthio-1-propyne (4). Some of the functionalization products were subjected to acidic hydrolysis affording the expected methyl ketones.
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  • 59
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 55-62 
    ISSN: 0009-2940
    Keywords: Diastereoselective hydrogenation ; Folic acid ; Immobilized optically active rhodium(I)/diphosphane catalysts ; Leucovorin ; HPLC analysis of 5-formyltetrahydrofolic acid derivatives ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For the hydrogenation of the C=N bonds in the pyrazine ring of the vitamin folic acid (1) optically active rhodium(I)/diphosphane complexes immobilized on supports such as silica gel or Al2O3 were used. The reduction was carried out at 50 bar hydrogen pressure in an aqueous solution buffered to pH 7. Thus, 5,6,7,8-tetrahydrofolic acid (2) was obtained which contains a new asymmetric center at C-6 of the pterine system. Therefore, in combination with the (S) configuration of the natural L-glutamic acid part of the molecule two diastereomers with (6S,S) and (6R,S) configuration arise. The relatively unstable tetrahydrofolic acid (2) was converted into its 5-formyl derivative folinic acid (4) by treatment with methyl formate/formic acid in a 5:1 mixture of DMSO/pyridine. The Ca salt of folinic acid (4) is the widely used drug leucovorin. The diastereomers were separated by silica gel HPLC. To the column bovine serum albumine (BSA) is covalently bound. With optically active rhodium(I)/diphosphane catalysts, immobilized on silica gel supports, a diastereoselectivity of up to 90% could be achieved in the hydrogenation of folic acid (1).
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  • 60
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 405-408 
    ISSN: 0009-2940
    Keywords: Hexahydro-closo-hexaborates ; Boron ; Bridging ligands ; NMR spectroscopy ; Gold ; Copper ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By reaction of (PPh3)3 CuCl and PPh3AuCl with [B6H6]2- in organic media, dinuclear complexes are formed containing the hexaborate as a bridging ligand coordinated to the metal centers by opposite B3 facets of the B6 cluster in a trihapto mode. This is verified by single-crystal X-ray structural analysis of the isotypical (Paā) compounds [Cu2μ-bis-η3-B6H6)(PPh3)2] (1) and [Au2(μ-bis-η3-B6H6)(PPh3)2)] (2) which showed the metal centers to be very close to the B3 plane [1.92 (1), 2.10 (2) Å. The 11B NMR spectra of the two compounds feature doublets, at δ= -15.32 in 1 and at -11.51 in 2, which are significantly shifted downfield in comparison to [B6H6]2- (δ= -17.2).
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  • 61
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 425-429 
    ISSN: 0009-2940
    Keywords: Silver complexes ; Crown compounds ; Thioethers ; 1,3-Dithioles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The coordination chemistry of two crown thioethers 2,5,8,10,12-pentathiabicyclo[7.3.0]dodeca-1)9)-ene-11-thione (L) and -11-one (L') with Ag1 has been investigated by structural methods. Both thioethers act as tridentate ligands coordinating the silver ion in a trigonal fashion. In the case L, the 11- thione sulfur is coordinated additionally by another silver ion, to yield a polymeric chain with a distorted-tetrahedral geometry about the metal ion. Despite differing only in its carbonyl chalcogen, L' forms six-coordinated, monomeric complexes.
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  • 62
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 433-442 
    ISSN: 0009-2940
    Keywords: Metallobiosites ; Metalloproteins ; Metalloenzymes ; Dinucleating ligands ; Transition metals ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Awareness of the asymmetric nature of numerous dinuclear metallobiosites and of the ability of the individual metal ions to have quite distinct roles in the functioning of the metalloenzyme concerned has led to a search for carefully designed unsymmetric dinucleating ligands that will give dinuclear complexes capable of acting as models for the metallobiosites. This review surveys progress made in the design and synthesis of complexes capable of serving as models for donor atom, coordination number and geometric asymmetries found at dinuclear metal centres.
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  • 63
    ISSN: 0009-2940
    Keywords: Alkali metal organophosphanylamide ; Carbon-potassium bonding ; Phosphazane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The metalation of bis(diphenylphosphanyl)amine [HN-(PPh2)2,1 with KOtBu at 95°C in toluene affords a pale yellow precipitate of potassium bis(diphenylphosphanyl)amide (3a). On addition of liquid N,N,N′,N“,N“-pentamethyldiethylenetriamine (PMDTA, 4) the precipitate dissolves in toluene at 115°C to give a yellow solution, from which yellow-green blocks of [(Ph2P)2NK·PMDTA] (3b) are obtained. X-ray analysis reveals that the coordination sphere of potassium consists of the chelating triamine ligand and [N(PPh2)2]- as N-donor as well as η1 and η2 C-donor with two phenyl fragments. No phosphorus coordination of [N(PPh2)2]- is observed.
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  • 64
    ISSN: 0009-2940
    Keywords: Phosphaalkynes ; Triorganoaluminium compounds ; Cooligomerization ; Cage compounds ; Aluminium compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When the trialkylaluminium reagents 5 are allowed to react with phosphaalkynes 4 in n-pentane, a highly selective phosphaalkyne cyclotrimerization with incorporation of two organometallic units occurs (→ 6). The tetracyclooctane derivatives 6a-e represent the first examples of phosphorus-aluminium-carbon cage compounds. The polycyclic products 6 are able to function as ligands in transition-metal complexes (→ 7), which is illustrated by the reactions of 6b, c with nonacarbonyldiiron and pentacarbonyl(tetrahydrofuran)tungsten, respectively.
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  • 65
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 283-289 
    ISSN: 0009-2940
    Keywords: Zinc ; Sulfonate ligands ; Perchlorates ; Coordination modes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Attempts are reported to incorporate sulfonate and perchlorate anions as ligands in zinc complexes of tripodal ligands. Using tris(benzimidazolylmethyl)amine (BIMA) only the aqua complexes [ (BIMA)Zn-OH2](RSO3)(ClO4) and [(BIMA)Zn-OH2](RSO3)2(R=CH3, CF3, p-tolyl) were accessible. Using substituted pyrazolylborates (Tp*), the same three sulfonate anions were found to be ligands in the complexes Tp*Zn-OSO2R. Spectroscopic evidence for perchlorate coordination in Tp*ZnClO4 · 2 DMSO conflicts with crystallograpic evidence against it in Tp*ZnClO4 · pyridine. The crystal structures of [(BIMA)Zn-OH2](CH3SO3)2, TpCum,MeZn-OS02CH3, TPtBu,MeZn-OSO2C6H4-p-CH3, and [TpCum,MeZn · NC5H5]ClO4 were determined.
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  • 66
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 295-298 
    ISSN: 0009-2940
    Keywords: Rhenium ; Oxides ; Alkyl ligands ; Dirhenium compounds ; Metal-metal interactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Most alkylrhenium(VII) oxides, e.g. ((cyclo)-C3H5)Re03 (2) are rather sensitive to temperature and moisture with the prominent exception of methyltrioxorhenium (1). The corresponding alkylrhenium(VI) oxides of formula [RR′(O)- Re(μ-O)]2 [R=R′=(cyclo)-C3H5 (3), iPr (4); R=CH3, R′=C2H5 (5), R=CH3, R′=iPr (6)] are much more stable in this regard. They can be handled in air at room temperature. They were synthesized from Re207 and dialkylzinc precursors, fully characterized and are available in much higher yields than their ReVII congeners. Mixed tetraalkyltetraoxodirhenium(VI) complexes (R # R′) synthesized from 1 and dialkylzinc compounds form as a mixture of cis/trans isomers. They are oily liquids at room temperature. The Re=O and Re-Re stretching force constants as a measure of the bond strengths, were determined from IR and Raman data.
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  • 67
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 335-340 
    ISSN: 0009-2940
    Keywords: Allylsilanes ; Superbases ; Metalations ; Stereoselectivity ; Cyclizations ; Silicon ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When treated with two equivalents of a butyllithium/potassium tert-butoxide mixture, terminal olefins carrying unprotected hydroxy or carboxy groups generate allylmetal intermediates which can be trapped with chlorotrimethylsilane to afford functionalized (Z)-2-alkenyltrimethylsilanes. One equivalent of the superbasic reagent suffices if the unsaturated alcohols are first protected as acetals before being subjected to the metalation/silylation/hydrolysis sequence.
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  • 68
    ISSN: 0009-2940
    Keywords: Metallacycloalkanes ; Metallacycloalkenes ; Osmium ; Iron ; Cyclic ketones ; Metallacycles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of the bis(triflates) [F3CSO3-(CH)m-O3SCF3] [m = 5-10, 12, 14, 16 (1a-i) with Na2[Os(CO)4] in dimethyl either affords the osmacycloalkanes 2a, 2b and 2f-i (m = 5, 6, 10, 12, 14, 16), diosmacycloalkanes 3a-i (m = 5-10, 12, 14, 16), and triosmacycloalkanes 4a-i (m = 5-10, 12, 14, 16). The structure of 3f was investigated by an X-ray structural analysis. This 22-membered disomacycle crystallizes in the space group Pā with Z = 1. If the unsaturated cis-4-octen-1,8-diyl bis(trifluoromethanesulfonate) (5) is treated with Na2[Os(CO)4] the diosmacyclooctadeca-5,14-diene 6 is obtained. By treating the bis(triflates) 1a, b with Na2[Fe(CO)4] the corresponding ferracycloalkanes are formed only in situ. Insertion of carbon monoxide into the M-C σ bonds leads to the cyclic ketones 7a, d and to the diketone 8d.
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  • 69
    ISSN: 0009-2940
    Keywords: Pyrrolidinephosphanes ; 3-Hydroxypyrrolidine ; 3-Diphenylphosphanylpyronlidine ; Salt effects ; Polymorphism ; Homogeneous catalysis ; Palladium ; Asymmetric catalysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation of both enantiomers of 3-diphenylphosphanulpyrrolidiine (2) and several N-substituted derivatives together with two PdIi complexes of this ligand is reported. Form L-malic acid and L-hydroxyproline both enantiomers of 3-hydroxypyrrolidine are prepared without any problems due to epimerization. KPPh2 in the presence of LiCl is shown to be the most effective reagent for the synthesis of 2. The reported X-ray structure determination sof Pdl2 complexes show a rather rigid bicyclic hetero-norbornane skeleton. The flexibility of the other parts of the molecules is obvious in several polymorphs revealed by this method. This polymorphism is additionally investigated by a 31P-CP-MAS study. From solution 1-, 13C- and 31P-NMR studies it is concluded that the bicyclic hetero-norbornane skeleton is retained in solution.
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  • 70
    ISSN: 0009-2940
    Keywords: Trichlorosilylation ; Dichlorophosphanes ; Silylphosphanes ; Amino(silyl)phosphanes ; Silicon /Reductions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of hexachlorodisilane and of trichlorosilane/triethylamine with alkyl-and dialkylaminodichlorophosphanes RPCl2 1a-i [R = iPr: a; (Me3Si)2CH: b; R=1-adamantly: c: R=tBu: d; R=Et2N: e; R=iPr2M: f] furnish bis(trichlorosilyl)-phosphanes RP(SiCl3)2 3a-f. However, when less bulky substituents are attached to the phosphorus atom, so that there is little steric crowding, the double reductive silylations leading from 1 to 3 are accompanied by side reactions and decomposition of 3. Therefore, only 3b, 3c, 3d, and 3f wre isolated in a pure state. These compounds are more readily prepared by the; trichlorosilane/triethylamine method. 1H-, 31P- and 29Si-Nmr spectra confirm their constitution. The structure of solid 3f, the first aminobis(trichlorosilyl)phosphane, was determined by X-ray crystallography. 3f contains a phosphorus atom in a pyramidal environment surrounded by two silicon atoms and a planar nitrogen atom of the diisopropylamino group.
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  • 71
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 417-420 
    ISSN: 0009-2940
    Keywords: Gallium ; Low-valent compounds ; Gallium-gallium bond ; Terminal triphenytriazenido ligand ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetrakis[bis(trimethylsilyl)methyl]digallane (4) 1 reacts with 1,3-diphenyltriazene to yield two compounds, which were both characterized by a crystal structure determination. The gallium-gallium bond is retained in the yellow derivate [(H5C6)2N3](R)Ga-Ga(R)[N3(C6H5)2 2 [R = CH(SiMe3)2], which is formed by a ligand exchange reaction and shows two terminal chelating triazenido ligands besides two bis(trimethylsilyl)methyl groups; the Ga—Ga bond length is 245.79(6) pm. The second product is the orange dialkyl(diphenyltriazenido)gallium derivative R2Ga[N3(C6H5)2] 3, where the triazene has reacted as an oxidant by the cleavage of the Ga—Ga bond and probably by release of elemental hydrogen.
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  • 72
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 463-472 
    ISSN: 0009-2940
    Keywords: Hypervalent compounds ; Tellurium ; Polycations ; Molecular Orbital Theory ; Band structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Approximate MO and band structure calculation are used to analyze the bonding in the recently synthesized paramagnetic, semiconducting phase [Te15Br4]2+. The [Te15Br4]2+ chains are very similar to those in the tellurium subhalide Te2Br. The electronic structure and bonding within these chains is analysed and the possibility of hypervalency in both [Te15Br4][MoOBr4]2 and Te2Br is discussed. The bonding in the classically hypervalent molecule TeBr42- and a model Te3Br24- is compared to that of the infinite system. Our calculations indicate that both [Te15Br4][MoOBr4]2 and Te2Br contain weakly hypervalent Te atoms and that the interesting electronic properties of [Te15Br4][MoOBr4]2 arise within the distinct sublattices, which do not interact significantly.
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  • 73
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 479-488 
    ISSN: 0009-2940
    Keywords: Heterobimetallic complexes ; Carbene complexes ; Alkynes ; Coupling reaction ; Bridging ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sequential reaction of the dimethylamino(trimethylsilylethylnyl)carbene complexes [(CO)5M'=C(NMe2)C≡CSiMe3] [M' = W (1a)] with KF/THFMeOH, nBuLi and transition metal halides, [XMLn], affords heterobimetallic propynyliden complexes of the type [(CO)5M'=C(N-Me2)C≡CMLn] [MLn = Ni(PPh3) Cp (4a, b). Ni(PMe2Ph)2- {Mes) (Mes=2,4,6-C6H2Me3) (5a), Rh(CO)(PPh3)2 (6a), Fe(CO)2Cp (7a,b)]. In contrast, reaction of 1a with MeLi · LiBr and [IFe(CO)2Cp] yields the novel N-metallated complex [(CO)5W=C{N(ME)Fe(CO)2Cp}C≡CSiMe3] (8a). The complexes [(CO)5M'=C(NMe2)C≡CMLn=Fe(CO)2Cp (7a, b), Ru(CO)2Cp (10a,b), Ru(CO)(PPh3)Cp (11a), Mn(CO)5 (12a), Re(CO)5 (13a)] are accessible by Pd-catalyzed coupling of the C-stannylated carbene complexes [(CO)5M'=C-(NMe2)C≡CSnBu3] (9a, b) with [XMLn]. The related monomethylaminocarbene complexes [(CO)5M'=C(NHMe)C≡ CSnBu3] (16a, b), obtained by stannylation of [(C))5M'=C(NHMe)C=CH] (15a, B) with Bu3SnNEt2, react with [IFe(CO)2Cp] to give the bimetallic complexes [(CO)5M'=C(NHMe)C≡CFe(CO)2Cp] (17a, b). The complexes 4a, 5a, 7a and 10a were characterized by X-ray structural analysis. The spectroscopic and structural data suggest that the two metal centers in 4-7, 10-13, and 17 interact only weakly.
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  • 74
    ISSN: 0009-2940
    Keywords: Rhenium ; Technetium ; 8a-Amino-6-methyl-ergoline ; Chelates ; Structure elucidation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Current research in radiopharmaceutical chemistry is aimed at the design of technetium-based receptor-binding radiotracers because of the excellent nuclide properties of the isotope 99mTc. Tc tracers and the corresponding complexes of rhenium, as the inactive surrogate of Tc, are required to imitate organic agonists or antagonists of the receptor. We have started studies with ergolines, which are known to be dopamine substitutes. The present report deals with the functionalization of 8α-amino-6-methyl-ergoline (2) with a 2-mercaptoacetyl group, and the subsequent synthesis of the first rhenium complex containing a pendent ergoline moiety [Re- O(SSS)(RS)] (HSSSH = HS-CH2CH2-S-CH2CH2-SH and RSH = 8a-amino-N-(2-mercaptoacetyl)-6-methyl-ergoline) (4). The molecular structure of the rhenium complex was determined by X-ray crystal structure analysis.
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  • 75
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 859-862 
    ISSN: 0009-2940
    Keywords: Yttrium ; Lanthanum ; Samarium ; Lanthanides ; Aminotroponiminate ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of N-isopropyl-2-(isopropylamino)troponimine, [(i-Pr)2ATI]H, with KH in THF affords [(i-Pr)2ATI]K. This is a useful starting material for the preparation of the mono-, bis- and tris-substituted compounds [[i-Pr)2ATI]YCl2-(THF)2}2, [(i-Pr)2ATI2Y[O(2,6,t-Bu2C6H3)] and [(i-Pr)2-ATI]3Ln (Ln = Y, La, Sm), which can be obtained from ([i-Pr)2ATI]K and LnX3 and LnX3 (X = Cl, I), or Y[O(2,6-t-BuC6H3)]3. All compounds have been characterized by spectroscopic methods. The monosubstituted yttrium complex {[(i-Pr)2ATI]YCl2(THF)2}2 has also been investigated by single crystal X-ray diffraction.
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  • 76
    ISSN: 0009-2940
    Keywords: C-H activation ; Alkyne complexes ; Cyclopentadienyl cobalt ; Fluxionality ; Hydrido complexes ; Clusters ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vicinal C-H bonds of the cycloalkenes CnH2n (n = 5-8) were activated upon treatment under mild conditions with reactive sources of the (C5H5)CO fragment. With [C5H5)CO(C2H4)2] (2a), the trinuclear cluster complexes [H2((C5H5)CO)3(μ3-C2(CH2)n-2)] (5a: n = 5; 5c: n = 5d: n = 8) were formed. Using the more reactive [(C5H5)2Co]/K, 5a-5dwere obtained, along with small amounts of the tetranuclear [{(C5H5)CO}4r{μ4-C2(CH2)n-2}] (8a-c: n = 5-7). X-ray structure analyses of 5c, d and 8b, c were performed. A μ-‖ (orμ3-η1:η2:η1) coordination of the cycloalkyne ligands was found in the trinuclear cluster complexes. The tetranuclear 8b, c had the cycloalkynes quadruply bridging (μ4-η1:η2:η2:η1_ a butterfly arrangement of the metal atoms. The acetylenic carbon-carbon bonds are considerably lengthened upon coordination [1.392(4), 1.398(3) å in 5c d; 1.464(8), 1.499(5) Å in 8b, c]. Three dynamic processes - alkyne “walk” on top of the CO3 triangle, μ2-hydride migration, and μ2/μ3-hydride exchange - are operational in the trinuclear 5a-d. Dynamic NMR data for 5a are consistent with a “windshield-wiper” mechanism for the alkyne migration. Hydride exchange is associated with a higher energy barrier, and is probably and independent dynamic process.
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  • 77
    ISSN: 0009-2940
    Keywords: Mercury ; Lanthanides ; Lanthanoid(II) complexes ; (N-2,6-Diisopropylphenyl)(N-trimethylsily)amide complexes ; Bis(trimethylsilyl)amide complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Mercury(II) amide complex Hg[N(SiMe3)(2,6-iPr2C6H3)]2 (1) was prepared by reaction of HgBr2 with Li[N(SiMe3) 2,6-iPr2C6H3)] in diethyl ether solvent. Redox transmetallation reactions of 1 with elemental samarium, europium or ytterbium in THF solvent (THF = tetrahydrofuran), generated the novel divalent complexes Ln[N(SiMe3)(2,6-iPr2C6H3]2(THF)2 with Ln = Sm (2), Eu (3) and Yb (4). 4 was also synthesized by reaction of elemental ytterbium, HgPh2 and HN(SiMe3)(2,6-Me3)2]2(THF)2 [Ln = Sm (5), Yb (6)] by reaction of the metals with HgPh2 and HN(SiMe3)2. Thermal desolvation of 4 under high vacuum gave Yb(N)(SiMe3)2,6-iPr2C6H3)]2 (THF) (7), whereas under identical conditions 6 yielded the solvent-free complex [Yb[N{SiMe3)2]2]2. (8). The new compounds 1-4 and 7 are hydrocarbon soluble and 171Yb-NMR spectra were recorded for 4, 6, 7 and 8. X-ray crystal structure determinations of 2 and 4 revealed four-coordinate, distorted tetrahedral metal environments augmented by weak Ln…ipso-C(aryl) interactions.
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  • 78
    ISSN: 0009-2940
    Keywords: Biaryls ; Boron ; Chirality ; Cooperative Effects ; Lewis acids ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A number of Lewis acid binaphthyl systems, substituted in 2-or 2,2′-position, are synthesized by lithiation of 2,2′-dibromo-1,l ′-binaphthyl (5), followed by addition of various electrophiles. Stepwise lithiation and subsequent borylation with trimethyl borate leads to the bromoboronic acid 6, which can be stabilized by esterification with pinacol giving 7. By increasing the reaction mixture to 2 equiv. of n-butyllithium and 2 equiv. of methyl borate the path to the binaphthylmonoboronic acid ester 9 is opened up. A further increase in the quantity of electrophile also leads to the binaphthylbisboronic acid ester 12. The 2,2′-disubstituted silyl, germyl, and stannyl derivatives 13a-15a are accessible in good yields. Treatment with boron halides leads exclusively to methyl/halogen exchange, giving the bidentate Lewis acids 13b-15b, the former of which can be bridged by oxygen.Only in case of the bis(tributylstannyl)binaphthyl 16a does ipso substitution occur in the presence of boron trichloride, giving the bis(dichloroboryl)-substituted binaphthyl 16b which can then be hydrolysed to 11. The structures of the majority of the compounds were investigated by X-ray diffraction. In case of the 2,2′-disubstituted compounds 13a-15a the naphthyl groups are orientated perpendicular to each other. The intra- and intermolecular interactions are dominated by this binaphthyl system. In case of the oxygenbridged compounds 13c and 14c the angle between the naphthyl planes decreases to about 70°. This also has an effect on the packing of the molecule; in this instance the orientation of two naphthyl in neighbouring molecules is nearly parallel. The structure of the diboronic acid is dominated by intra- and intermolecular hydrogen bonding.
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  • 79
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 951-954 
    ISSN: 0009-2940
    Keywords: Phosphane-boranes ; Medium-sized rings ; Ring opening and closure ; Temperature-dependent NMR studies ; Phosphorus ; Boron ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A phosphane-borane (3) with the P-B bond integrated into a seven-membered ring was prepared from 4-pentenyl-diphenylphosphane (4) by hydroboration using 9-borabicyclononane (9-BBN). The product was confirmed to have a ring structure in the solid state by single crystal X-ray diffraction. The P-B distance of 2.057(2) Å is indicative of a standard donor-acceptor bond similar to the type found in homologous five- and six-membered rings. The room-temperature 31P-NMR signal of the compound in various solvents (δ ≈ - 15) is not compatible with the cyclic structure and suggests that ring opening occurs as the compound is dissolved. Variable-temperature NMR work corroborated this assumption, and the enthalpy of ring closure was determined to be ΔH = -30.5(4) kJmol-l. In CD2C12 at -90°C, δ31P is shifted to +3.5 ppm to low field, suggesting virtually complete ring closure under these conditions.
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  • 80
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 963-968 
    ISSN: 0009-2940
    Keywords: Fluorine ; Macrocycles ; Complexes ; Sodium ; Barium ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two new fluoro macrocycles BenzoFN2O3 and F(N2O2)2C2H4 were synthesized in the reactions of 1,3-bis(bromomethyl)-2-fluorobenzene with benzo-diaza-15-crown-5 and 1,2-bis(diaza-12-crown-4)ethane, respectively, in 30% yield each. Close CF...metal ion interactions in the respective alkaline metal complexes in solution are evidenced by characteristic shifts of the 19F-NMR resonances of up to δ = 18.7 relative to the free ligand and by a decrease of the 1J(CF) coupling constant of up to 20 Hz, which is most pronounced in BenzoFN2O3 · Li+ and F(N2O2)2C2H4 · K+. In BenzoFN2O3· Li+ a1J(19F-7Li) of 15.5 Hz was observed, which is indicative very close CF...Li+ interactions in solution. In the X-ray crystal structures of BenzoFN2O3 · Na+ [CF⃛Na+ 246.8(2) pm], 26-fluoro-4,7,13,16-tetraoxa-1, 10-diazatricyclo[ 8.8.7.1 20,24 ] - hexacosa-20,22,24(26)triene · Na+ (CF⃛Na+ 267.1(2) pm) and 21 -fluoro-3,6,9,12,15,18-hexaoxabicyclo[ 18.3.1 1,20]heneicosa- l(24),20,22-triene. Ba2+ [CF⃛Ba2+ 299.0(3) pm] short CF⃛metal interactions were found. Such close CF⃛metal ion interactions do not result in a lengthening of the C-F bonds, which is not a sign of weak CF⃛metal ion interactions, since a Cambridge Structural Database search revealed that a shortening of the C-O bond length is also not observed in crown ether complexes of alkaline metals.
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  • 81
    ISSN: 0009-2940
    Keywords: Phosphorus heterocycles ; 1H-Phosphirenes ; Nucleophilic substitution reactions at 1H-phosphirenes ; Metal-complexation of functionalized 1H-phosphirenes ; Carbonyl complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The halogen atoms in the 1-chloro-1H-phosphirenes, 5a-c, are easily substituted on reaction with organolithium and Grignard reagents, 14a-p, with formation of the corresponding O-, N-, C-, Si-, and Ge-substituted 1H-phosphirenes, 15a-t. C1/H exchange reactions also occur on reaction with lithium metal hydrides (5a → 17). Furthermore, substitution reactions are also realized with the alkali metal borates, 18a-g (→19a-g); the same is true for reactions with trimethylsilyl cyanide and azide (→22a-d). Some of the substitution products have been characterized in the form of their metal complexes, 16, 23, 24, and 25.
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  • 82
    ISSN: 0009-2940
    Keywords: Germatranes ; Organotrihalogenogermanes ; Organometallic (Si, Ge, Sn) reagents ; Transmetallation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Trialkylstannyl esters of tris(2-hydroxyalkyl)amines, N(CH2CHROSnAlk3)3 (9-11 (R = H, Me; Alk = Et, Bu), react with X3GeC(R1)(R2)COOR3 (12-17) (X = Cl or Br; R1, R2=H, Me, Ph, SiMe3, COOEt; R3=Me, Et) to give esters of α-germatranylcarboxylic acids, N(CH2CHRO)3GeC(R1)(R2)-COOR3 (1-8), in high yields. The synthesis of esters 12-17 is reported. Esters of α-germatranyldiphenylacetic acid 24 and 25 can be obtained by treatment of diphenylketene with Et3SnOMe to give in situ Et3SnC(Ph2)COOMe (23), followed by reaction with GeCl4 to give in situ Cl3GeC(Ph2)COOMe (22 and further reactions with 9 or 11, respectively. Reduction of germatrane 6 with LiAlH4 in diethyl ether leads to cleavage of the germanium-carbon bond with subsequent formation of (2-hydroxyethyl)trimethylsilane. The crystal structures of 3, 6 and 7 are reported. 1-Acyloxygermatranes 26 and 27 are obtained by treatment of 1-methoxygermatrane (28) with diphenyl- and dichloroacetic acid, respectively.
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  • 83
    ISSN: 0009-2940
    Keywords: Tin - Nitrogen cage compounds ; Sn—X—Sn intramolecular bridges ; Distannylamine pyridine adduct ; Tin ; Moessbauer spectroscopy ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tris(dimethylchlorostannyl)amine (2a) reacts with pyridine in a 3:4 molar ratio to produce the tin-nitrogen containing bicyclo[3.1.1]heptane (3) with elimination of the adduct Me2SnCl2·2 py. Treatment of the distannylamine 2,6-[Pr2H3N(SnMe2Cl)2 (4) with pyridine, however, leads to the formation of the 1:1 pyridine adduct 4 and this can be regarded as a model to explain the route to 3. The molecular structures of 3 and 5 were determined by multinuclear magnetic resonance spectroscopy in solution, as well as by X-ray structure analysis of their crystals. Typical structural features for both compounds are intramolecular Sn—X—Sn bridges. Support for the structures comes from MS fragmentation patterns, IR spectra, and the Mössbauer spectra.
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  • 84
    ISSN: 0009-2940
    Keywords: 1,2,4-Diazaphospholes ; Phosphiranes, alkylidene- ; 2-Phosphabutadienes ; Phosphorus heterocycles ; pyrazolines, thermolysis ; Rearrangements ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 5-alkylidene-4,5-dihydro-3H-1,2,4(λ3)-diazaphospholes (4-phosphapyrazolines) are thermally much more stable than related compounds without the exocyclic double bond. Thermolysis reactions typically occur in the range 110-150°C in toluene solution, and different, mostly competing, reaction pathways are observed. Thermal extrusion of nitrogen from 8a-g gives rise to β-phosphanaylsiloxyalkenes 10, benzo[c]-phosphole derivatives 11, 14 and 115, (β-siloxyalkylidene)-Phosphiranes 12, and dihydro-1,3-oxaphospholes 13. The thermolysis of 5-alkylidene-4,5-dihydro-4-trimethylsilyl-3-trimethylsilyloxy-3H-1,2,4-dizaphospholes 17 afforded three products, including the highly substituted and stable 2-phosphabutadienes 18 formed by nitrogen extrusion and rearrangement. Finally, the 4-chloro-3-trimethylsilyloxy-substituted heterocycle 21 was transformed at 170°C into 4H-1,2,4-diazaphosphole 23. The structures of 13c and 18a were determined by single-crystal X-ray diffraction.
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  • 85
    ISSN: 0009-2940
    Keywords: Boron ; Diazaboroles ; Carbenes ; Heterocycles ; Imidazoles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Bromo-2,3-dihydro-1H-1,3,2-diazaboroles (3a-c) were synthesized by cyclocondensation of dilithiated 1,4-diazabutadienes (5a-c) with boron tribromide in hexane. 3a was also obtained by sodium amalgam reduction was conducted in ether solvents, diboroxane (2) resulted as the main product. Compound 3a and 1,3-dialkyl-4,5-dimethylimidazol2-ylidenes (6a, b) underwent halide displacement to afford the borolylimidazolium salts 7a, b. Compounds 2, 3a-c, and 7a, b were characterized by elemental analyses and spectroscopic methods (1H, 11B, 13C NMR; Ir; MS). The molecular structures of 2 and 7a were established by single-crystal X-ray diffraction analyses.
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  • 86
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 725-728 
    ISSN: 0009-2940
    Keywords: Dendrimers ; Metal complexes ; Nanostructures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Strong multiple complexation of transition metal ions, Cu(II), Zn(II) and Ni(II) with different generations of well-defined poly(propylene imine) dendrimers as multi(tridentate) ligands has been used to construct nanoscopic assemblies of defined structure and size incorporating a distinct number of metal ions from 2 up to 32.
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  • 87
    ISSN: 0009-2940
    Keywords: Germanium ; Digermenes ; Tin ; Germylenes ; Stannylenes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of GeCl2 · dioxane with the Grignard reagent RMgBr (R=2-tBu-4,5,6-Me3C6H) furnishes the tetraaryldigermene R2Ge=GeR2 (8). X-ray structure-analysis of 8 reveals a short Ge=Ge double bond, a nearly planar environment of both germanium atoms and extremely widened C—Ge—C angles of 128°. In solution, 8 dissociates into two germylene molecules R2Ge, which can be trapped with oxygen or by [4+1] cycloaddition reactions with 1,4-dihetero-1,3-dienes. A similar cycloadduct of a stannylene wa obtained by thermolysis of (R′2Sn)3 (R′=2,4,6-iPr3C6H2), in the presence of a 1,4-diazabutadiene and characterized by an X-ray structure-analysis.
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  • 88
    ISSN: 0009-2940
    Keywords: Silicenium ion ; Iminosilane ; Aluminate ; Silicon ; Aluminium ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Lithiated text-butylaminolfluorosilanes react with aluminum trichloride in ether, eliminating LiF to give AlCl3 adducts of iminosilanes  -  aminosiliceniotrichloroaluminates {R2Si-NCMe3·AlCl3}, which thermally form the dimethylazomethine- aluminium trichloride, Me2C=NH·AlCl3.
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  • 89
    ISSN: 0009-2940
    Keywords: Titanocene complexes ; S ligands ; Organic polysulfanes ; Ligand transfer reactions ; Sulfur heterocycles ; Chalcogens ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of Cp2Ti(CO)2 (3) with the di- and polysulfanes 1,2,4-(CH2)2S3, C4S6 (9), C,7H10S3 (11), 1,2,4,6-(CH2)3S4 (16), C6H10S6(19), and S6 affords the titanocene chelate complexes Cp2TiS3(CH2)2 (8), (Cp2Ti)2C4S6 (10), Cp2TiS3C7H10 (13), Cp2TiS2C7H10 (14), Cp2TiS4(CH2)3 (17), Cp,2TiS6C6H6H10 (20), and Cp2TiS8 (23). 14 is also obtained from Cp2TiCl2 (1) and the geminal dithiol of norbornene. The analogous reaction with the dithiol of dicyclopentadiene yields Cp2TiS2C10H12 (15). In ligand transfer reactions, 8 reacts with SCl2 to give 1,2,3,5-tetrathiane (25), 10 provides 9 on reaction with Cl2, 13 when treated with S2Cl2 affords C7H10S5 (12), 15 reacts with S2Cl2Cl2 to give C10H12S4. 17 and SCl2 yield 1,2,3,5,7-pentathiepane (18), 20 is converted to C6H10S7 (22) on reaction with SCl2, and 23 yields S10 and 1,2,-C6H4(SCl)2, respectively. With phosgene, thiophosgene, and thionyl chloride, compound 15 yields the corresponding dithiocarbonate 26, the trithiocarbonate 27 and the trisulfane 2-oxide 28. The structure of 27 was determined by X-ray crystallography.
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  • 90
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 801-806 
    ISSN: 0009-2940
    Keywords: Unsymmetrical phthalocyanines ; Hemiporphyrazines ; Macrocyclic bisdienes and bisdienophiles ; Diels-Alder reactions ; Ladder polymers ; Cycloaddition ; Macrocycles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The specific synthesis of a metal-free bisdienophilic phthalocyanine 193, suitable for repetitive Diels-Alder reactions, is reported. This was achieved by condensation of 191,3,3-trichloro-6/7-nitroioindolenine (191) and 4,9-dibutoxy-2,3,5,8-tetrahydro-1,3-diimino-1H-5,8-epoxybenz[f]isoindoline (2). The ability of 3 to undergo Diels-Alder reactions was tested by reaction with an excess of 1,2,3,4-tetraphenylcyclopentadienone (5). Experimental data of the hemiporphyrazines 9, 10, and 11, which can be used as precursors for the synthesis of ladder polymers, are also given in the Experimental Section.
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  • 91
    ISSN: 0009-2940
    Keywords: Platinum ; Nitrocyanamide ; Nitrosodicyanomethanide ; 1,1,3, 3-Tetracyano-2-azapropenide ; 1,1,2,3,3-Pentacyanopropenide ; Hydrido complexes ; Coordination modes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new coordination compounds trans-[Pt(H)X(PPh3)2] with NCN- and C(CN)2-functionalized anions (X- = [N(O)C(CN)2]-, [NO2NCN]-, [N{C(CN)2}2]-, [NCC{C-(CN)2}2]-, have been characterized by 1H-, 31P-, 13C-NMR, and IR spectroscopy and elemental analyses the crystal structures of trans-[Pt(H)N(O)C(CN)2(PPh3)2], trans- [Pt(H)N{C(CN)2}2(PPh3)2], and trans-[Pt(H)NCC{C(CN)2}2-(PPh3)2) have been determined by X-ray diffraction. Remarkably, [N(O)C(CN)2]- is coordinated through the central nitrogen atom, while [N{C(CN)2}2]- and [NCC(C(CN)2]2]- are bonded through terminal nitrogen atoms of a C(CN)2 unit.
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  • 92
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    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1021-1027 
    ISSN: 0009-2940
    Keywords: Zinc ; Chirality ; Cross-coupling ; Phosphorylations ; Catalysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This Microreview on the chemistry of organozinc reagents starts by briefly showing the methods of preparation of organozinc compounds and then discusses the considerable synthetic utility of zinc organometallics for the formation of new carbon-carbon bonds in the presence of transition-metal catalysts. Finally, the use of organozinc chemistry for the preparation of polyfunctional and chiral phosphanes is described.
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  • 93
    ISSN: 0009-2940
    Keywords: Bis(tetramethylipiperidino)aluminum halides ; Alkoxy((tetramethylpiperidino)aluminum halides ; 27Al-NMR spectra ; Aluminum ; Amides ; Synthetic methods ; Bridging ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-Lithio-2,2,6,6-tetramethylpiperidine [Li(tmp)] reacts with AlX3 (X = Cl, Br) in diethyl ether/ n-hexane solution to generate the products of substitution and ether cleavage, [tmpAl(X)(μ-OEt)], (la, X = Cl; 1b, X = Br). However, when the reaction is allowed to proceed in n-hexane alone, an almost quantitative yield of compounds tmp2AlX (2a, X = Cl; 2b, X = Br; 2c, X = I) is obtained. According to 27AI-NMR spectroscopy, mass spectroscopy, cryoscopy, and X-ray crystal structure determinations, these compounds are monomeric in the solid state, in solution, and in the gas phase. 2b reacts with AgBF4 yielding the fluoride-bridged dimer (tmp2AlF), 2d, as shown by X-ray crystal structure determination.
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  • 94
    ISSN: 0009-2940
    Keywords: Planar-tetracoordinate carbon ; Dynamic organometallic systems, μ-alkyne complexes ; π-Agostic systems ; Zirconium ; Metallocenes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The benzonitrile hydrozirconation product Cp2ZrCl(N—CHPh) 8 was treated with propynyl lithium to yield the (propynyl)(benzaldimido)ZrCp; complex 9. Subsequent treatment with trityl tetraphenylborate generated [Cp2Zr(C—C—CH3)-BPh-4] that instantaneously added to 9 to eventually form the (μ-aldimido)(μ-η1:η2-hexadiyne)ZrCp2 cation 11. The X-ray crystal structure analysis showed that 11 contains a planar-tetracoordinate carbon atom that is stabilized by forming a three-center-two-electron bond with the two adjacent metal atoms. Similarly, complex 9 reacted with [Cp2Zr(CH3)+CH3B(C6F5)3 1 to yield the planar-tetracoordinate carbon containing (μ-aldimido)(μ-η1:η2-2-butyne) Cp; cation 12. Both complexes 11 and 12 exhibit dynamic NMR spectra due to their rapid reorganization of the dimetallabicyclic frameworks (ΔG* = 10 kcal mol-1) in addition to an anchimerically assisted C—N bond rotation (ΔG* =15 kcal mol-1).
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  • 95
    ISSN: 0009-2940
    Keywords: Porphyrinatomanganese(IV) ; Monooxygenase model ; Dichloro monoxide ; Catalytic alkene epoxidation ; Catalytic alkane oxygenation ; Catalytic alkane chlorination ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The isolation at -78°C and characterization of the novel crystalline reactive porphinatomanganese(IV) complex Mn-(TDCPP)(OCl)2 (5) is described. 5 is compared with the porphinatomanganese(IV) complexes Mn(TDCPP)(C6H5IOCl)2 (2), Mn(TDCPP)(C6F510C1)CI (3) and Mn(TDCPP)(OCH3)2, (4). The stoichiometric reaction of 5 with triphenylphosphane yields 2.5 equivalents of triphenylphosphane oxide and 1.0 equivalent of Mn(TDCPP)Cl (1). Complex 5 epoxidizes stilbene, and oxygenates and chlorinates cyclohexane.
    Additional Material: 2 Tab.
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  • 96
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1135-1139 
    ISSN: 0009-2940
    Keywords: Arene complexes ; Chromium ; Allenes ; Rearrangements ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Cr(CO)3-complexed η6-phenylpropargylic alcohols 3 react in a displacement rearrangement with thionyl chloride or chlorodiphenylphosphane to give the chloro- or phosphoryl allenyl substituted η6-phenyl complexes 4 and 6, respectively. In the X-ray crystal structure of the novel organometallic allenic derivatives 4b and 6b the vicinal chloro or phosphoryl substituent and the benzene(tricarbonyl)chromium fragment are arranged coplanarily. Palladium/copper-catalyzed couplings of the chloroallene 4b with terminal alkynes disclose a facile access to ynallene derivatives 8, novel carbon-rich organometallic π-systems.
    Additional Material: 1 Ill.
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  • 97
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1141-1145 
    ISSN: 0009-2940
    Keywords: Trichlorophosphoranylidenesulfamoyl chloride ; Vibrational spectroscopy ; Conformational properties ; Quantum chemical calculations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Raman (3500-50 cm-l) and infrared (4000-400 cm-l) spectra of the title compound, ClSO2N=PCl3, were recorded for the solid and liquid phase. Additionally, the Raman spectrum of the compound dissolved in CCl4 was obtained and qualitative depolarization values were determined. The spectra of the liquid and solid phase were interpreted in terms of the existence of only one conformation possessing C1 symmetry, as predicted by quantum chemical calculations. A complete vibrational assignment is proposed based on the relative intensities, on group frequencies along with support from the normal coordinate analysis. The experimental fundamental vibrational modes are compared to those obtained from theoretical approaches employing the ab initio MP2/6-31G* method and a density functional approximation (B3PW91/6-31G*).
    Additional Material: 3 Ill.
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  • 98
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1147-1150 
    ISSN: 0009-2940
    Keywords: Icosahedral heteroboranes ; Ab initio calculation ; Bonding models ; Aromaticity ; Nucleus Independent Chemical Shift [NICS] ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ab initio theoretical studies on X2B10H10 (X = CH, SiH, N, P and Sb) have been done for all the three possible isomers. Unlike lower-vertex heteroboranes, all the hetero derivatives have shown similar trends in the relative stabilities, the 1,12-isomer being more stable followed by 1,7- and 1,2-isomers, except for N and Sb. No conventional 1,2-isomer for N could be found. Instead, a new nido isomer which is 18.1 kcal/mol higher in energy than the most stable isomer has been located. Any hetero group substitution to icosahedral R12H122- is found to be thermodynamically destabilizing. However, the Nucleus Independent Chemical Shift criterion shows that all compounds, except for 8, have similar aromaticity.
    Additional Material: 2 Tab.
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  • 99
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1159-1166 
    ISSN: 0009-2940
    Keywords: Aminosilantes ; Structure elucidation ; Molecular conformations ; Configuration determination ; Nitrogen Planarity/Silanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structural chemistry of a series of triaminosilanes XSi(NR2)3 has been investigated in order to determine the ground-state configuration and conformation of these molecules. Theoretical studies and analogy with the isoelectronic XP(NR2)3 (X = CH2, O, Se, NSiMe3 etc.) and P(NR2)3 molecules suggest structures of Cs or C3 symmetry, with small energy differences between them. The molecular structure of HSi(NMe2)3 (1) has been determined by a single-crystal X-ray diffraction study at low temperature. Surprisingly, the molecules have a non-standard conformation with an irregular orientation of the three NMe2 groups. The hydrido-, chloro-, methyl-, and vinyltris(morpholino)silanes XSi[N(CH2CH2)2O]3 (X = H, Cl, Me, Vi; 2-5) were prepared from the corresponding chlorosilanes and morpholine (2, 3) or lithium morpholide (4,5). Their variable-temperature NMR spectra were studied and the molecular structures determined by single crystal X-ray diffraction. Compound 2 has a molecular geometry approaching mirror symmetry with one morpholino group significantly different from the other two. This structure resembles that of isoelectronic tris(amino)phosphines. Compounds 3-5 have structures with a propeller-like arrangement of the three morpholino rings approaching C3 symmetry for this part of the molecules. The chloro compound 3 shows the shortest Si-N bond lengths (average 1.690 Å), followed by 2 (1.708Å),5 (1.709Å) and 4 (l.712Å). The configuration of all nitrogen atoms is almost planar, with sums of the angles close to 360°, and the morpholino rings adopt a chair conformation. According to the solution NMR spectra the ring inversion is slow at low temperature, but the rings rotate freely about the Si-N bonds on the NMR time scale. The molecular structures are discussed in terms of steric and electronic effects of the substituents. Other model compounds, including (Me2N)3SiC6H4-4-Br (6), MeSi[N(CH2CH2)2NMe]3 (7) and PhSi[N(CH2)4]3 (8), could not be crystallized, but were characterized by their analytical and spectroscopic data.
    Additional Material: 7 Ill.
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  • 100
    ISSN: 0009-2940
    Keywords: Lead ; Tetrachloroaluminate ; Arenes ; o-Xylene ; Bis(arene) Complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis(o-xylene)lead(II) bis(tetrachloroaluminate), obtained from lead(II) chloride and aluminium trichloride in o-xylene, has been shown by X-ray crystallography to be a mononuclear lead complex with point group symmetry C2 The two aromatic ligands are arranged similarly to those in monomeric plumbocene. The coordination sphere is completed by two bidentate AlCl4-ions. The lead center uses about a quarter of its bonding capability for each of the four ligands
    Additional Material: 1 Ill.
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