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  • Chemistry  (4,188)
  • Limnology
  • General Chemistry
  • Cell & Developmental Biology
  • 2020-2024  (50)
  • 2000-2004  (485)
  • 1945-1949  (4,111)
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  • 1
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    EDP SCIENCES
    Publication Date: 2024-04-05
    Description: Chemistry
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry
    Language: French
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  • 2
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    EDP SCIENCES
    Publication Date: 2024-04-05
    Description: Chemistry
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry
    Language: French
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  • 3
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    EDP SCIENCES
    Publication Date: 2024-04-07
    Description: Chemistry
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry
    Language: French
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  • 4
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    Springer Nature | Springer International Publishing
    Publication Date: 2024-04-05
    Description: Chilean Patagonia, located at the southwestern tip of South America, is one of the last regions on earth where highly intact environments predominate. With a coastline that extends along some 100,000 km of fjords, channels, and islands, it has one of the world´s most extensive marine-terrestrial interfaces. Local place-based and Indigenous cultures and management practices are a vital presence across the region, while the long and rich history of conservation efforts have resulted in officially protected areas covering over 50% of the land and 41% of the coastal-marine area. However, Chilean Patagonia is increasingly facing anthropogenic pressures associated with increased infrastructure and access, salmon aquaculture, extractive industries, and the spread of invasive exotic species. Despite widespread recognition that Chilean Patagonia represents a unique global reservoir of socio-natural heritage, to date there has been no region-wide assessment of the scientific evidence of the conservation status of its ecosystems or the priorities for their effective conservation. Conservation in Chilean Patagonia: Assessing the state of knowledge, opportunities, and challenges is the first book to gather and synthesize the available scientific and socio-environmental information related to Patagonian conservation. It presents the collaborative work of 68 researchers and local experts, representing a range of specialties and perspectives, including: biology, ecology, socio-ecology, fisheries, aquaculture, anthropology, economics, geography, tourism, cryosphere, oceanography, climate and global change. The book’s 18 chapters focus on the status of key ecosystems and conservation tools, and provide recommendations toward the construction of a renewed, inclusive, and integrated conservation agenda for the Chilean Patagonian region. It provides an essential primer for anyone interested in the future of this ecologically vital region, as well as lessons on interdisciplinary collaboration and integrated analysis of conservation issues useful for conservation practitioners and scholars. This is an open access book. This book is a translation of an original Spanish edition. The translation was done with the help of artificial intelligence (machine translation by the service DeepL.com). A subsequent human revision was done primarily in terms of content, so that the book will read stylistically differently from a conventional translation.
    Keywords: Ecology ; Limnology ; Oceanography ; Biodiversity ; Marine-terrestrial Interface ; thema EDItEUR::P Mathematics and Science::PS Biology, life sciences::PSA Life sciences: general issues::PSAF Ecological science, the Biosphere ; thema EDItEUR::R Earth Sciences, Geography, Environment, Planning::RN The environment::RNK Conservation of the environment ; thema EDItEUR::R Earth Sciences, Geography, Environment, Planning::RB Earth sciences::RBK Hydrology and the hydrosphere::RBKC Oceanography (seas and oceans) ; thema EDItEUR::R Earth Sciences, Geography, Environment, Planning::RG Geography::RGM Biogeography ; thema EDItEUR::R Earth Sciences, Geography, Environment, Planning::RN The environment::RNC Applied ecology::RNCB Biodiversity
    Language: English
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  • 5
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    Springer Nature | Springer International Publishing
    Publication Date: 2024-01-16
    Description: Chilean Patagonia, located at the southwestern tip of South America, is one of the last regions on earth where highly intact environments predominate. With a coastline that extends along some 100,000 km of fjords, channels, and islands, it has one of the world´s most extensive marine-terrestrial interfaces. Local place-based and Indigenous cultures and management practices are a vital presence across the region, while the long and rich history of conservation efforts have resulted in officially protected areas covering over 50% of the land and 41% of the coastal-marine area. However, Chilean Patagonia is increasingly facing anthropogenic pressures associated with increased infrastructure and access, salmon aquaculture, extractive industries, and the spread of invasive exotic species. Despite widespread recognition that Chilean Patagonia represents a unique global reservoir of socio-natural heritage, to date there has been no region-wide assessment of the scientific evidence of the conservation status of its ecosystems or the priorities for their effective conservation. Conservation in Chilean Patagonia: Assessing the state of knowledge, opportunities, and challenges is the first book to gather and synthesize the available scientific and socio-environmental information related to Patagonian conservation. It presents the collaborative work of 68 researchers and local experts, representing a range of specialties and perspectives, including: biology, ecology, socio-ecology, fisheries, aquaculture, anthropology, economics, geography, tourism, cryosphere, oceanography, climate and global change. The book’s 18 chapters focus on the status of key ecosystems and conservation tools, and provide recommendations toward the construction of a renewed, inclusive, and integrated conservation agenda for the Chilean Patagonian region. It provides an essential primer for anyone interested in the future of this ecologically vital region, as well as lessons on interdisciplinary collaboration and integrated analysis of conservation issues useful for conservation practitioners and scholars. This is an open access book. This book is a translation of an original Spanish edition. The translation was done with the help of artificial intelligence (machine translation by the service DeepL.com). A subsequent human revision was done primarily in terms of content, so that the book will read stylistically differently from a conventional translation.
    Keywords: Ecology ; Limnology ; Oceanography ; Biodiversity ; Marine-terrestrial Interface ; bic Book Industry Communication::R Earth sciences, geography, environment, planning::RN The environment::RNK Conservation of the environment ; bic Book Industry Communication::P Mathematics & science::PS Biology, life sciences::PSA Life sciences: general issues::PSAF Ecological science, the Biosphere ; bic Book Industry Communication::R Earth sciences, geography, environment, planning::RG Geography::RGM Biogeography ; bic Book Industry Communication::R Earth sciences, geography, environment, planning::RN The environment::RNC Applied ecology::RNCB Biodiversity
    Language: English
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  • 6
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    EDP SCIENCES
    Publication Date: 2024-04-05
    Description: Chemistry
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry
    Language: French
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  • 7
    Publication Date: 2024-04-05
    Description: Chemistry
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry
    Language: French
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  • 8
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    EDP SCIENCES
    Publication Date: 2024-04-08
    Description: Chemistry
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry
    Language: French
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  • 9
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    EDP SCIENCES
    Publication Date: 2024-04-05
    Description: Chemistry;Materials science
    Keywords: Chemistry ; Materials science ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry
    Language: French
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  • 10
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    EDP SCIENCES
    Publication Date: 2024-04-05
    Description: Chemistry
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry
    Language: French
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  • 11
    Publication Date: 2024-04-22
    Description: A preliminary inventory of the composition of zooplancktonic species found in Bayano Lake, between February and September 1981 revealed that there are seven species of Rotifera, five Cladocera, two Copepoda, one Ostracoda and larvae of Macrobrachium (Decapoda) and Chaoborus (Diptera). The composition, abundance and horizontal and monthly distribution of the most important zooplanktonic groups found in Bayano Lake are here presented.
    Description: Published
    Description: Refereed
    Keywords: Limonology ; Abundancia ; Vertical distribution ; Limnology ; Composición
    Repository Name: AquaDocs
    Type: Journal Contribution
    Format: pp.17-24
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  • 12
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Mineralogy includes thirteen chapters that discuss the methodology of specific mineralogical methods, the composition of minerals from different igneous rocks, and the composition of minerals from different sedimentary rocks.It contains detailed mineralogical studies from Africa, Asia, and Europe. Chapters present different scientific mineralogical methods and detailed descriptions of minerals from different magmatic and sedimentary rocks.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNV Chemistry of minerals, crystals and gems
    Language: English
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  • 13
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Benzimidazole is a comprehensive survey of the known and new methods of benzimidazole synthesis, the spectral and theoretical aspects of existing benzimidazole derivatives, and the anticancer properties of a new class of benzimidazole derivatives. This book examines aspects and newer mechanisms of benzimidazoles containing heterocyclic moiety. Chapters report on anticancer properties of benzimidazole derivatives, novel methods of synthesis of benzimidazoles, versatile nature of the benzimidazoles, spectral and theoretical studies of benzimidazole derivatives, and medicinal importance and pharmacological aspects of benzimidazole derivatives.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry
    Language: English
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  • 14
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Green Chemistry - New Perspectives is at the frontiers of this continuously evolving interdisciplinary science, and publishes research that attempts to reduce the environmental impact of the chemical enterprise by developing a technology base that is inherently non-toxic to living things and the environment. The book covers all aspects of green chemistry, including chemical synthesis, nano synthesis, eco-friendly processes, biomass, extraction techniques, environmental remediation, and energy, making it a unique reference resource. This will continue to encourage scientists around the world to develop novel synthetic methods or improve the existing ones to circumvent some of the problems and favours all aspects of green chemistry. This book is intended for academia, professionals, scientists, as well as graduate and undergraduate students without any geographical limitations.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry
    Language: English
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  • 15
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: This book consists of several selected chapters on important subjects in modern high-performance liquid chromatography (HPLC) and ultra-performance liquid chromatography (UPLC). The content addresses aspects related to both improvements in the mainstream HPLC/UPLC technology and utilization, as well as developments of exploratory new materials and equipment. The book presents useful details about the presented subjects as well as describes new applications and/or relevant case studies for each subject. It is addressed to a large audience of analytical chemists involved in separation science. Each chapter is authored by scientists with considerable field and academic experience.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNF Analytical chemistry
    Language: English
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  • 16
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Recent Advances in Chemical Kinetics provides a comprehensive overview of several types of chemical reactions. It includes six chapters that discuss solvent catalysis, customized flow reactors, p-conjugation in kinetics, kinetics of autoxidation, molecular chameleon for cations and anions, and internal clocks of atoms.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNR Physical chemistry
    Language: English
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  • 17
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Redox reactions are involved in biochemistry, energy, corrosion, and much more. In both biology and electrochemistry, the redox reaction is complex and varied. For example, redox shuttles in supercapacitors show aspects of molecular electrochemistry applied to electrode porosity. In pseudocapacitors, the formalism associated with their electrochemical response requires investigation and formalism. Similarly, the simple definition of redox potential opens fundamental questions about its measurement in solutions without supporting salts. This book illustrates the variety of redox reactions in its examination of the importance of redox molecules in the development of new electrical energy storage devices.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNR Physical chemistry::PNRH Electrochemistry and magnetochemistry
    Language: English
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  • 18
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: We are living in a critical time, both for humanity and the planet, which has led us to look for more sustainable formulas to interact with the environment. One of the important changes in the design and operation of chemical processes is the search for environmentally friendly technologies. Supercritical carbon dioxide has been revealed as a promising environmentally friendly solvent that is energy efficient, selective and capable of reducing waste, making it a promising alternative to conventional organic solvents. However, reliable and versatile mathematical models of phase equilibrium thermodynamics are needed for the use of supercritical carbon dioxide in process design and viability studies. This book reviews experimental procedures for obtaining high-pressure phase equilibria data and describes the phase diagrams of binary mixtures and some thermodynamic models capable of determining the conditions of phase equilibria at high pressures. These concepts are applied to the components of the transesterification reaction of rac-2-pentanol with a vinyl ester, which is important in the pharmaceutical industry because (S)-2-pentanol can be obtained as a reaction product. This product is a key intermediate in the synthesis of drugs against Alzheimer’s disease.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNR Physical chemistry
    Language: English
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  • 19
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: In recent decades, artificial porous structures have attracted increasing enthusiasm from researchers inspired by the fascinating molecular pores in nature and their unique biological functions. Although substantial achievements in porous materials have been realized, the construction of topologically designed pores is still challenging. Recently, the emergence of covalent organic frameworks (COFs), which are constructed based on organic and polymer chemistry, has made it possible to design artificial pores with controlled pore size, topology and interface properties. COFs are crystalline porous materials constructed by the precise reticulation of organic building blocks via dynamic covalent bonds. Distinct from non-covalent interactions which tend to produce isostructures, covalent bonds enable accurate pore design owing to their predetermined reaction pathways. In addition, the appropriate polycondensation of organic building units enables the formation of extended two-dimensional (2D) and three-dimensional (3D) polymer architectures with periodically ordered skeletons and well-defined pores. With their large surface area, tailorable structures, and tunable chemistry, COFs are regarded as potentially superior candidates for various applications including catalysis, energy storage and conversion, mass transport and biotechnology. This book examines the historic achievement of COFs, providing clear and comprehensive guidance for researchers on their structural design, synthetic protocols and functional exploration.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry
    Language: English
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  • 20
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Fluoride covers a continuum of topics that are frequently studied in the broad area of fluoride (F) research. It provides an overview of the primary sources of environmental fluoride in typical high-fluoride environments and demonstrates the transitions and transformations that emerge and culminate in hydro-geochemical interactions that result in fluoride-fouling of large portions of the world’s water and agricultural resources. This way, the book pinpoints the connection between F enrichment of water sources and the prevalence of endemic fluorosis in certain areas of the world. In order to contribute to a better understanding of the global fluoride problem, new fluoride detection and quantification technologies are proposed with an in-depth analysis of emerging trends in the use of portable user-friendly devices in point-of-use measurements of water fluoride. This has been presented against the backdrop of a robust overview of traditional fluoride quantification methodologies that are still in wide application among the scientific communities. In addressing fluoride toxicities, which are not limited to dental and skeletal dilapidations, the authors have explored the role of natural antioxidants in ameliorating physiological fluoride-induced noxious effects in mammalian systems. Nonetheless, since community dependence on high-fluoride water due to a lack of alternative clean water sources remains to be the principal pathway of human fluoride over-exposure, a review chapter on F mitigation techniques applied all over the world is incorporated aiming at providing a succinct overview of water defluoridation techniques and strategies being used to combat the impacts of human F overexposure around the globe. Since every cloud has a silvery lining, the possibility of using ammonium fluorides as a novel reagent in mineral processing has been considered convenient industrial fluorinating agents, which present the possibility of complete regeneration that is not afforded by the reagents presently used in decomposing silicon component of the ores.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNK Inorganic chemistry
    Language: English
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  • 21
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: This book discusses the chemistry and applications of pyridine derivatives. The library of pyridine derivatives is growing steadily with numerous synthetic analogues already described and the identification of new, naturally occurring pyridine-based compounds. The book includes ten chapters organized into two parts. The first part focuses on the numerous types of reactions that arise from pyridine derivatives. The second part examines the pharmaceutical applications of pyridine derivatives as well as their usefulness as sensors for metal cations and extracting agents for platinum group metals.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry
    Language: English
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  • 22
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: The book discusses multiple issues associated with modern dosimetry in physics and treatment planning and how investigators from diverse world centers and institutions approach problem-solving in these important areas. It examines topics including pretreatment validation and factors affecting reference dosimetry. It also addresses unique issues affecting pediatric populations as well as the modern role of thermoluminescence validation. Several chapters discuss intensity modulation, including defining modern problems associated with both treatment planning and the definition of tumor and normal tissue contours. Furthermore, the book examines the role of imaging as both a vehicle to define tumor targets and normal tissue as well as a tool for dose validation.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNR Physical chemistry::PNRL Nuclear chemistry, photochemistry and radiation
    Language: English
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  • 23
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: The book comprises 14 chapters covering all the issues related to water desalination. These chapters emphasize the relationship between problems encountered with the use of feed water, the processes developed to address them, the operation of the required plants and solutions actually implemented. This compendium will assist designers, engineers and investigators to select the process and plant configuration that are most appropriate for the particular feed water to be used, for the geographic region considered, as well as for the characteristics required of the treated water produced. This survey offers a comprehensive, hierarchical and logical assessment of the entire desalination industry. It starts with the worldwide scarcity of water and energy, continues with the thermal - and membrane-based processes and, finally, presents the design and operation of large and small desalination plants. As such, it covers all the scientific, technological and economical aspects of this critical industry, not disregarding its environmental and social points of view. One of InTech's books has received widespread praise across a number of key publications. Desalination, Trends and Technologies (Ed. Schorr, M. 2011) has been reviewed in Corrosion Engineering, Science & Technology – the official magazine for the Institute of Materials, Minerals & Mining, and Taylor & Francis's Desalination Publications. Praised for its “multi-faceted content [which] contributes to enrich it,” and described as “an essential companion...[that] enables the reader to gain a deeper understanding of the desalination industry,” this book is testament to the quality improvements we have been striving towards over the last twelve months.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNF Analytical chemistry
    Language: English
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  • 24
    Publication Date: 2024-04-05
    Description: The Global Methane Initiative (GMI) is a voluntary international partnership that promotes methane recovery and reuse activities in developing and transition economies. The U.S. Department of State requested an evaluation of the activities and outcomes supported in whole or in part by its contributions to GMI to gauge its value added to the program.
    Keywords: Physics ; Environmental Science ; Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TQ Environmental science, engineering and technology ; thema EDItEUR::R Earth Sciences, Geography, Environment, Planning::RB Earth sciences::RBP Meteorology and climatology
    Language: English
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  • 25
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Progress in agricultural, biomedical and industrial applications' is a compilation of recent advances and developments in gas chromatography and its applications. The chapters cover various aspects of applications ranging from basic biological, biomedical applications to industrial applications. Book chapters analyze new developments in chromatographic columns, microextraction techniques, derivatisation techniques and pyrolysis techniques. The book also includes several aspects of basic chromatography techniques and is suitable for both young and advanced chromatographers. It includes some new developments in chromatography such as multidimensional chromatography, inverse chromatography and some discussions on two-dimensional chromatography. The topics covered include analysis of volatiles, toxicants, indoor air, petroleum hydrocarbons, organometallic compounds and natural products. The chapters were written by experts from various fields and clearly assisted by simple diagrams and tables. This book is highly recommended for chemists as well as non-chemists working in gas chromatography.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNF Analytical chemistry
    Language: English
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  • 26
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: This book discusses electrocatalysis and electrocatalysts for energy, water electrolysis, water treatment, CO2 conversion, and green chemistry. It reviews various electrocatalysts and their properties and electrochemical performances. The first section of the book covers topics in direct alcohol fuel cells including Pt-based electrocatalysts as non-carbon electrode support materials and the development of electrocatalysts for direct methanol fuel cells. The second section of the book covers various topics in electrocatalysis and electrocatalysts for a cleaner environment, including electrocatalysts for the conversion of CO2 to valuable products and SYNGAS, electrocatalysts for water electrolysis, and much more.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNR Physical chemistry::PNRH Electrochemistry and magnetochemistry
    Language: English
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  • 27
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Surfactants are ubiquitous and have applications in diverse areas, including food, cosmetics, detergents, lubricants, enhanced oil recovery (EOR), and targeted drug delivery systems. Their wide diversity of applications owes to their unique structure, namely, a hydrophilic and a hydrophobic group present in the same molecule. Although most surfactants used industrially are synthetic, there is a growing need for natural surfactants, as the latter is obtainable from renewable sources and are less toxic and highly biodegradable in contrast to their synthetic counterparts. This book is a compilation of interesting articles by various experts that cover various applications of both synthetic and natural surfactants.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNR Physical chemistry::PNRC Colloid chemistry
    Language: English
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  • 28
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: The chemical sensor plays an essential role in the fields of environmental conservation and monitoring, disaster and disease prevention, and industrial analysis. A typical chemical sensor is a device that transforms chemical information in a selective and reversible way, ranging from the concentration of a specific sample component to total composition analysis, into an analytically useful signal. Much research work has been performed to achieve a chemical sensor with such excellent qualities as quick response, low cost, small size, superior sensitivity, good reversibility and selectivity, and excellent detection limit. This book introduces the latest advances on chemical sensors. It consists of 15 chapters composed by the researchers active in the field of chemical sensors, and is divided into 5 sections according to the classification following the principles of signal transducer. This collection of up-to-date information and the latest research progress on chemical sensor will provide valuable references and learning materials for all those working in the field of chemical sensors.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNF Analytical chemistry
    Language: English
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  • 29
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Distillation is an important separation technique that has been used for many centuries to exploit the volatility differences between components in a mixture. The distillation process has many variations and applications. This book includes two sections on desalination and reactive distillation. It discusses desalination in the processes of solar and membrane distillation, with a focus on the reduction of energy costs to obtain potable water. It also discusses reactive distillation, which can be used in some cases to reduce the power duty in the separation process by using the reaction heat directly in the separation. The book includes cases of mathematical modeling, simulation, and optimization of the distillation process.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNF Analytical chemistry
    Language: English
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  • 30
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Cyclodextrins (CDs) have attracted great interest from the research community as well as industries in an array of sectors because of their unique structural features. This book provides a comprehensive overview of CDs, beginning with their historical background. Chapters address such topics as the structure and physiochemical properties of CDs, advancements in the field, and potential applications of these materials in fields such as drug delivery and sensing. This book reveals new frontiers in the CD world and is a useful resource for organic, analytical, and supramolecular chemists as well as scientists engaged in biological and material sciences.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry::PNNP Polymer chemistry
    Language: English
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  • 31
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: The book presents a comprehensive overview of sorption, which is a multi-parametric separation process. It is extensively used in the removal of various pollutants from the tertiary stage of wastewater treatment, from leachates, etc. It discusses fundamental points of the technique as well as kinetic theories and isotherms. It also examines the synthesis and characterizations of all studied adsorbent materials to find their paths of sorption. Finally, it highlights the importance of having a cost-estimation plan for the synthesis of sorbent materials as well as predictions for their reusability.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNR Physical chemistry::PNRX Surface chemistry and adsorption
    Language: English
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Carotenoids are natural and versatile secondary metabolites, most of them showing colours that vary from yellow to red. They are widespread among living beings where they are involved in many biological roles reporting beneficial actions. To date, more than 750 carotenoids have been described in nature. Humans cannot synthesize carotenoids de novo, thus they are mainly obtained through diet. In fact, carotenoids are consistently found in tissues or biological fluids where they play a beneficial decreasing the risk of developing some diseases.During the last half-century, significant advances in carotenoids research have been made. This book highlights new perspectives and applications of carotenoids including characterization and isolation of new compounds (including rare carotenoids), their production at a mid-large scale (involving new innovative approaches), and uses of carotenoids in different biotechnological fields like food science, biomedicine, and cosmetics.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNN Organic chemistry
    Language: English
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  • 33
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    IntechOpen | IntechOpen
    Publication Date: 2024-04-05
    Description: Infrared Spectroscopy - Perspectives and Applications is a compendium of contributions from experts in the field of infrared (IR) spectroscopy. This assembly of investigations and reviews provides a comprehensive overview of the fundamentals as well as the groundbreaking applications in the field. Chapters discuss IR spectroscopy applications in the food and biomedicine sectors and for measuring transport through polymer membranes, characterizing lignocellulosic biomasses, detecting adulterants, and characterizing enamel surface advancements. This book is an invaluable resource and reference for students, researchers, and other interested readers.
    Keywords: Chemistry ; thema EDItEUR::P Mathematics and Science::PN Chemistry::PNF Analytical chemistry::PNFS Spectrum analysis, spectrochemistry, mass spectrometry
    Language: English
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  • 34
    Publication Date: 2023-03-08
    Description: © The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in LeClerc, H., Tompsett, G., Paulsen, A., McKenna, A., Niles, S., Reddy, C., Nelson, R., Cheng, F., Teixeira, A., & Timko, M. Hydroxyapatite catalyzed hydrothermal liquefaction transforms food waste from an environmental liability to renewable fuel. IScience, 25(9), (2022): 104916, https://doi.org/10.1016/j.isci.2022.104916.
    Description: Food waste is an abundant and inexpensive resource for the production of renewable fuels. Biocrude yields obtained from hydrothermal liquefaction (HTL) of food waste can be boosted using hydroxyapatite (HAP) as an inexpensive and abundant catalyst. Combining HAP with an inexpensive homogeneous base increased biocrude yield from 14 ± 1 to 37 ± 3%, resulting in the recovery of 49 ± 2% of the energy contained in the food waste feed. Detailed product analysis revealed the importance of fatty-acid oligomerization during biocrude formation, highlighting the role of acid-base catalysts in promoting condensation reactions. Economic and environmental analysis found that the new technology has the potential to reduce US greenhouse gas emissions by 2.6% while producing renewable diesel with a minimum fuel selling price of $1.06/GGE. HAP can play a role in transforming food waste from a liability to a renewable fuel.
    Description: This work was funded by the DOE Bioenergy Technology Office (DE-EE0008513), a DOE DBIR (DE-SC0015784) and the MassCEC. The authors thank WenWen Yao, Department of Environmental Science at WPI, for TOC analysis, Mainstream Engineering for heating value characterization of the oil and solid samples, Wei Fan for assistance in obtaining SEM images and, Julia Martin and Ronald Grimm for their assistance in collecting XPS data, and Jeffrey R. Page for his assistance with oil upgrading and analysis. HOL was partially funded for this work by NSF Graduate Research Fellowship award number 2038257. A portion of this work was performed at the National High Magnetic Field Laboratory Ion Cyclotron Resonance user facility, which is supported by the NSF Division of Materials Research and Division of Chemistry through DMR 16-44779 and the State of Florida.
    Keywords: Chemistry ; Chemical engineering ; Catalysis
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 35
    Publication Date: 2024-02-26
    Description: Identifcation of ontogenetic age classes plays an important role in the felds of zoology, palaeontology and archaeology, where accurate age classifcations of (sub)fossil remains are a crucial component for the reconstruction \nof past life. Textural ageing\xe2\x80\x94the identifcation of age-related bone surface textures\xe2\x80\x94provides a size-independent \nmethod for age assessment of vertebrate material. However, most of the work so far is limited to qualitative results. \nWhile qualitative approaches provide helpful insights on textural ageing patterns, they are heavily subject to observer \nbias and fall short of quantitative data relevant for detailed statistical analyses and cross-comparisons. Here, we present a pilot study on the application of 3D surface digital microscopy to quantify bone surface textures on the long \nbones of the grey heron (Ardea cinerea) and the Canada goose (Branta canadensis) using internationally verifed \nroughness parameters. Using a standardised measuring protocol, computed roughness values show a strong correlation with qualitative descriptions of textural patterns. Overall, higher roughness values correspond to increased numbers of grooves and pits and vice versa. Most of the roughness parameters allowed distinguishing between diferent \nontogenetic classes and closely followed the typical sigmoidal animal growth curve. Our results show that bone \ntexture quantifcation is a feasible approach to identifying ontogenetic age classes.
    Keywords: General Physics and Astronomy ; General Environmental Science ; General Biochemistry ; Genetics and Molecular Biology ; General Materials Science ; General Chemistry ; Roughness ; Surfaces ; Taphonomy ; Topography ; Bone ; Ontogeny ; Digital microscopy
    Repository Name: National Museum of Natural History, Netherlands
    Type: info:eu-repo/semantics/article
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  • 36
    Publication Date: 2024-04-05
    Description: Chemiebezogene Kompetenzen werden bereits im Sachunterricht der Grundschule entwickelt und sollen im Chemieunterricht der Sekundarstufe I aufgegriffen und weiterentwickelt werden. Ziel dieser Studie war es, die chemiebezogenen Kompetenzen der Schülerinnen und Schüler in der Übergangsphase zwischen Sachunterricht und Chemieunterricht zu analysieren. In einer Ergänzungsstudie wurden zusätzlich sowohl die Auswirkungen der Schulschließungen aufgrund der SARS-CoV-II Pandemie auf die Kompetenzen der Schülerinnen und Schüler als auch der Einfluss einer veränderten Testadministration untersucht. Insgesamt wurden die Kompetenzen von 2262 Lernenden der Jahrgangsstufen 5 bis 9 zu drei Messzeitpunkten analysiert. Die Ergebnisse zeigen, dass die chemiebezogenen Kompetenzen sowohl zum Ende der Grundschulzeit als auch zu Beginn des Chemieunterrichts über alle Kompetenzbereiche hinweg sehr heterogen ausfallen. Dennoch sind sie zu Beginn des Chemieunterrichts in einigen Kompetenzbereichen höher ausgeprägt als zum Ende der Grundschulzeit. Nach den pandemiebedingten Schulschließungen waren die Kompetenzen ähnlich ausgeprägt wie in den gleichen Jahrgangsstufen vor den Schulschließungen. Eine während der Schulschließungen notwendige Bearbeitung der Testhefte von zu Hause aus führte vor allem bei den jüngeren Schülerinnen und Schülern zu besseren Testergebnissen als die Bearbeitung in der Schule. Um die Entwicklung chemiebezogener Kompetenzen in der Übergangsphase zu optimieren, sollte der Erwerb dieser Kompetenzen bereits im Sachunterricht einheitlicher gestaltet werden.
    Keywords: Science ; Chemistry ; Education ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::J Society and Social Sciences::JN Education
    Language: German
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    Logos Verlag Berlin | Logos Verlag Berlin
    Publication Date: 2024-04-05
    Description: In 2005, the hybrid model was published by Prof. H.-D. Alber and Prof. P. Zhu as an alternative to the Allen-Cahn model for the description of phase field transformations. With low interfacial energy, it is more efficient, since the resolution of the diffuse interface is numerically broader for the same solution accuracy and allows coarser meshing. The solutions of both models are associated with energy minimisation and in this work the error terms introduced in the earlier publications are discussed and documented using one and two dimensional numerical simulations. In the last part of this book, phase field problems, initially not coupled with material equations, are combined with linear elasticity and, after simple introductory examples, a growing martensitic inclusion is simulated and compared with literature data. In addition to the confirmed numerical advantage, another phenomenon not previously described in the literature is found: with the hybrid model, in contrast to the examples calculated with the Allen-Cahn model, an inclusion driven mainly by curvature energy does not disappear completely. The opposite problem prevents inclusions from growing from very small initial configurations, but this fact can be remedied by a very finely chosen diffuse interface width and by analysing and adjusting the terms that generate the modelling errors. The last example shows that the hybrid model can be used with numerical advantages despite the above mentioned peculiarities.
    Keywords: Science ; Chemistry ; Mathematics ; Science ; Physics ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PB Mathematics ; thema EDItEUR::P Mathematics and Science::PH Physics
    Language: English
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  • 38
    Publication Date: 2024-04-05
    Description: Das selbstgesteuerte Experimentieren ist laut den nationalen Bildungsstandards sowie den Lehrplänen im Fach Chemie ein wichtiger Bestandteil der naturwissenschaftlichen Schulbildung. Offene Experimentierformen sind jedoch wenig etabliert. Um das selbstgesteuerte Experimentieren in die Unterrichtspraxis zu implementieren, wurde im Rahmen dieses Forschungsprojekts eine eintägige Lehrkräftefortbildung zur Konzeption von selbstgesteuerten Experimenten im Chemieunterricht durchgeführt. Dazu wurde ein literaturbasiertes Strukturierungskonzept entwickelt, mit dem die Lehrkräfte kochbuchartige Schulversuche zu selbstgesteuerten und kompetenzorientierten Experimenten mit beliebigen Öffnungsgraden modifizieren können. Begleitend zur Fortbildung wurde im Prä-Post-Follow-Up-Design das fachdidaktische Wissen der Teilnehmenden hinsichtlich der Planung von selbstgesteuerten Experimenten empirisch überprüft. Zur Erfassung dieses Konstrukts wurde ein neues Messinstrument literaturbasiert entwickelt und die Güte des Messinstruments evaluiert. Die Auswertungen zeigen, dass die Fortbildung hinsichtlich des fachdidaktischen Wissens der Lehrkräfte kurz- sowie langfristig lernförderlich ist und die Fortbildung von den Teilnehmenden positiv bewertet wird. Die Reliabilitätsanalyse sowie die Validierungsstudie zeigen, dass der Test sowohl reliabel als auch valide ist. In Folgestudien könnte die langfristige Verhaltensänderung der Lehrkräfte bezüglich der Implementierung des selbstgesteuerten Experimentierens in den Unterricht untersucht werden.
    Keywords: Science ; Chemistry ; Science ; Education ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PD Science: general issues ; thema EDItEUR::J Society and Social Sciences::JN Education
    Language: German
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    Logos Verlag Berlin | Logos Verlag Berlin
    Publication Date: 2024-04-05
    Description: Konsumgüter werden beispielsweise mit Slogans wie "Gut in Bio. Schlecht in Chemie." beworben. Dabei wird intendiert, sich gezielt von "Chemie" abzugrenzen und sich das positive Bild von "Natur" zu Nutze zu machen. Dies prägt die öffentliche Meinung und trägt zu einer antagonistisch-wertenden Sicht von "Chemie" und "Natur" bei. Dass Chemie als Naturwissenschaft der Beschreibung der Natur dient, um deren Stoffe und Stoffumwandlungen zu erklären, ist dem Laien selten bewusst. Chemie findet überall statt, insbesondere in der Natur! Genau an diesem Punkt setzt das Unterrichtskonzept "Chemie Pur - Unterrichten in der Naturglqq an. Ziel ist es, im Freiland, mit direkt vor Ort gewonnenen Naturstoffen, Umweltprozesse experimentell zu erarbeiten. Die projektbegleitende Evaluationsstudie stellte sich der Forschungsfrage, wie sich das Unterrichtskonzept auf das Fach- und Sachinteresse, auf die Naturverbundenheit sowie auf die Einstellung zu Chemie und Natur von Schülerinnen und Schülern der Sekundarstufe II auswirkt. Die Auswertung der Fragebogenergebnisse mit latenten Veränderungsmodellen haben gezeigt, dass die Intervention im Freiland das inhaltsbezogene Sachinteresse steigert und die Einstellung zu Chemie und Natur positiv beeinflusst sowie ein erhöhten Fachwissenszuwachs ermöglicht. Die gewonnenen Erkenntnisse können die Grundlage für die Entwicklung und Evaluation von good-practice-Ansätzen naturwissenschaftlicher Lernsituationen bilden. Das Unterrichtskonzept Chemie Pur leistet zudem einen Beitrag im Bereich Outdoor Education, um den Antagonismus von Chemie und Natur zu verringern.
    Keywords: Science ; Chemistry ; Science ; Education ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::P Mathematics and Science::PD Science: general issues ; thema EDItEUR::J Society and Social Sciences::JN Education
    Language: German
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    The MIT Press | The MIT Press
    Publication Date: 2024-03-27
    Description: The original 1818 text of Mary Shelley's classic novel, with annotations and essays highlighting its scientific, ethical, and cautionary aspects. Mary Shelley's Frankenstein has endured in the popular imagination for two hundred years. Begun as a ghost story by an intellectually and socially precocious eighteen-year-old author during a cold and rainy summer on the shores of Lake Geneva, the dramatic tale of Victor Frankenstein and his stitched-together creature can be read as the ultimate parable of scientific hubris. Victor, “the modern Prometheus,” tried to do what he perhaps should have left to Nature: create life. Although the novel is most often discussed in literary-historical terms—as a seminal example of romanticism or as a groundbreaking early work of science fiction—Mary Shelley was keenly aware of contemporary scientific developments and incorporated them into her story. In our era of synthetic biology, artificial intelligence, robotics, and climate engineering, this edition of Frankenstein will resonate forcefully for readers with a background or interest in science and engineering, and anyone intrigued by the fundamental questions of creativity and responsibility. This edition of Frankenstein pairs the original 1818 version of the manuscript—meticulously line-edited and amended by Charles E. Robinson, one of the world's preeminent authorities on the text—with annotations and essays by leading scholars exploring the social and ethical aspects of scientific creativity raised by this remarkable story. The result is a unique and accessible edition of one of the most thought-provoking and influential novels ever written. Essays by Elizabeth Bear, Cory Doctorow, Heather E. Douglas, Josephine Johnston, Kate MacCord, Jane Maienschein, Anne K. Mellor, Alfred Nordmann
    Keywords: science fiction ; gothic ; horror ; European ; British ; literature ; fiction ; cautionary tale ; STEM ; science ; bioethics ; classic ; bicentennial ; Josephine Johnston ; Cory Doctorow ; Jane Maienschein ; Kate MacCord ; Alfred Nordmann ; Elizabeth Bear ; Anne K. Mellor ; Heather E. Douglas ; Frankenstein ; Creature ; Monster ; Mary Shelley ; Makers ; women in science ; science and anti-science ; values in science ; responsible innovation ; Industrial Revolution ; Mary Wollstonecraft ; William Godwin ; Percy Bysshe Shelley ; Galvanism ; Mount Tambora ; Myths ; Two Cultures ; epistolary novel ; Victor Frankenstein ; Geneva ; Prometheus ; Arctic ; Lord Byron ; John Polidori ; ghost stories ; Revisions ; Electricity ; Lightning ; Vitalism ; Chemistry ; Extinction ; Magnetism ; Moral responsibility ; Legal responsibility ; Social responsibility ; Consequences ; Obligations ; Ethics ; Maker Culture ; DIY ; Technology Adjacent Possible ; Facebook ; Surveillance ; Aristotle ; Fetal development ; Epigenesis ; Embryo ; Person ; Technoscience ; Alchemy ; uncanny valley ; animation ; complexity ; Morality ; Monstrosity ; Christianity ; Otherness ; Gender ; Nature ; Domestic Affections ; Women ; Sexuality ; Technical Sweetness ; Los Alamos ; Trinity Test ; Scientific Responsibility ; Nuclear Weapons ; adjacent possible ; synthetic biology ; robotics ; thema EDItEUR::F Fiction and Related items::FB Fiction: general and literary::FBC Classic fiction: general and literary ; thema EDItEUR::F Fiction and Related items::FL Science fiction::FLC Classic science fiction
    Language: English
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  • 41
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    Logos Verlag Berlin | Logos Verlag Berlin
    Publication Date: 2024-04-05
    Description: When auralizing moving sound sources in Virtual Reality (VR) environments, the two main input parameters are the location and radiated signal of the source. An array measurement-based model is developed to characterize moving sound sources regarding the two parameters in this thesis. This model utilizes beamforming, i.e. delay and sum beamforming (DSB) and compressive beamforming (CB) to obtain the locations and signals of moving sound sources. A spiral and a pseudorandom microphone array are designed for DSB and CB, respectively, to yield good localization ability and meet the requirement of CB. The de-Dopplerization technique is incorporated in the time-domain DSB to address moving source problems. Time-domain transfer functions (TDTFs) are calculated in terms of the spatial locations within the steering window of the moving source. TDTFs then form the sensing matrix of CB, thus allowing CB to solve moving source problem. DSB and CB are further extended to localize moving sound sources, and the reconstructed signals from the beamforming outputs are investigated to obtain the source signals. Moreover, localization and signal reconstruction are evaluated through varying parameters in the beamforming procedures, i.e. steering position, steering window length and source speed for a moving periodic signal using DSB, and regularization parameter, signal to noise ratio (SNR), steering window length, source speed, array to source motion trajectory and mismatch for a moving engine signal using CB. The parameter studies show guidelines of parameter selection based on the given situations in this thesis for modeling moving source using beamforming. Both algorithms are able to reconstruct the moving signals in the given scenarios. Although CB outperforms DSB in terms of signal reconstruction under particular conditions, the localization abilities of the two algorithms are quite similar. The practicability of the model has been applied on pass-by measurements of a moving loudspeaker using the designed arrays, and the results can match the conclusions drawn above from simulations. Finally, a framework on how to apply the model for moving source auralization is proposed.
    Keywords: Science ; Chemistry ; Technology & Engineering ; Construction ; Technology & Engineering ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TN Civil engineering, surveying and building::TNK Building construction and materials ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TB Technology: general issues
    Language: English
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  • 42
    Publication Date: 2024-04-05
    Description: Neuere Erkenntnisse zum Umsatzverhalten an Dieseloxidationskatalysatoren (DOCs) zeigen, dass das Umsatzverhalten von Schadstoffen vom Oxidationsgrad der verwendeten Edelmetallkatalysatoren abhängen kann. Dabei wird deutlich, dass sich der Oxidationsgrad bei typischen Abgaszusammensetzungen langsam und reversibel mit der Katalysatortemperatur ändert. Das kann bei periodischen Katalysatortemperaturänderungen zu einem ausgeprägten Hystereseverhalten führen. Bisherige Ergebnisse liegen insbesondere zum Verhalten der NO-Oxidation an Platin-Katalysatoren vor. Ziel der vorliegenden Arbeit ist es daher, die Untersuchungen auf seriennahe Pd- und PtPd-Mischkatalysatoren sowie auf andere abgastypische Schadstoffe, wie CO und Kohlenwasserstoffe, zu erweitern und dabei auch den Einfluss der Katalysatoralterung zu erfassen. Es wurde ein globalkinetisches Modell entwickelt und an die experimentellen Befunde angepasst. Dabei zeigte sich, dass es in der Regel möglich ist, das Umsatzverhalten bei reinen Pt- und Pd-Katalysatoren mit diesem örtlich eindimensionalen, makrokinetischen Zweiphasenmodell zutreffend zu beschreiben, wohingegen das Verhalten auf Pt/Pd-Mischkatalysatoren weniger gut simuliert werden kann. Dies ist vermutlich auf die heterogene Struktur der Pt/Pd-legierten Partikel zurückzuführen.
    Keywords: Science ; Chemistry ; Technology & Engineering ; Chemical & Biochemical ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TD Industrial chemistry and manufacturing technologies::TDC Industrial chemistry and chemical engineering
    Language: German
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  • 43
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    Taylor & Francis | CRC Press
    Publication Date: 2024-03-31
    Description: Hydroxyapatite coatings are of great importance in the biological and biomedical coatings fields, especially in the current era of nanotechnology and bioapplications. With a bonelike structure that promotes osseointegration, hydroxyapatite coating can be applied to otherwise bioinactive implants to make their surface bioactive, thus achieving faster healing and recovery. In addition to applications in orthopedic and dental implants, this coating can also be used in drug delivery. Hydroxyapatite Coatings for Biomedical Applications explores developments in the processing and property characterization and applications of hydroxyapatite to provide timely information for active researchers and newcomers alike. In eight carefully reviewed chapters, hydroxyapatite experts from the United States, Japan, Singapore, and China present the latest on topics ranging from deposition processes to biomedical applications in implants and drug delivery. This book discusses: Magnetron sputtering and electrochemical deposition The modification of hydroxyapatite properties by sol–gel deposition to incorporate other elements found in natural bones, such as zinc, magnesium, and fluorine The use of pure hydroxyapatite in drug delivery applications The growth or self-assembly of hydroxyapatite on shape memory alloy Hydroxyapatite composite coatings—with carbon nanotubes, titanium dioxide (TiO2), and others—on the titanium alloy Offering valuable insights and a wealth of data, including numerous tables and figures, this is a rich source of information for research on hydroxyapatite coatings. Each chapter also covers material that provides an accessible stepping stone for those who are new to the field.
    Keywords: Pre-clinical medicine: basic sciences ; Chemistry ; Materials science ; thema EDItEUR::M Medicine and Nursing::MF Pre-clinical medicine: basic sciences ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TG Mechanical engineering and materials::TGM Materials science
    Language: English
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  • 44
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    MDPI - Multidisciplinary Digital Publishing Institute
    Publication Date: 2024-04-05
    Description: Nanofibers, particularly those of a carbonaceous content, have received increased interest in the past two decades due to their outstanding physico-chemical characteristics and their possibility to form and contribute towards a plethora of potentially advantageous materials for consumer, industrial and medical applications. Despite this, and together with the numerous research studies and published articles that have sought to investigate these aspects, the potential impact of CNTs is still not understood. Whether or not nanofibers may be able to provide a sophisticated alternative to conventional materials is still debatable, whilst their effects upon both environmental and human health are highly equivocal. How nanofibers are conceived can determine how they may interact with different environments, such as the human body. Understanding each key step of the synthesis and production of nanofibers to their use within potential applications is therefore essential in gaining an insight into how they may be perceived by any biological system and environment. Thus, obtaining such information will enable all scientific communities to begin to realize the potential advantages posed by nanofibers. The aim of this Special Issue therefore, was to provide a collective overview of nanofibers; ‘from synthesis to application’. The Issue particularly focuses upon carbon-based nanofibers, but also highlights alternative nanofiber types. Emphasis is given holistically, with articles discussing the production routes of nanofibers, their plight during their life-cycle (origin to applied form and effects over time), as well as how nanofibers could either incite conflict, or provide aid to human and environmental health.
    Keywords: QD1-999 ; Toxicology ; Chemistry ; Biology ; Material Science ; Nanofibers ; Nanotechnology ; thema EDItEUR::P Mathematics and Science::PN Chemistry
    Language: English
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  • 45
    Publication Date: 2024-04-04
    Description: This volume, occasioned by the centenary of the Fritz Haber Institute, formerly the Institute for Physical Chemistry and Electrochemistry, covers the institute's scientific and institutional history from its founding until the present. The institute was among the earliest established by the Kaiser Wilhelm Society, and its inauguration was one of the first steps in the development of Berlin-Dahlem into a center for scientific research. Its establishment was made possible by an endowment from Leopold Koppel, granted on the condition that Fritz Haber, well-known for his discovery of a method to synthesize ammonia from its elements, be made its director. The history of the institute has largely paralleled that of 20th-century Germany. It undertook controversial weapons research during World War I, followed by a "Golden Era" during the 1920s, in spite of financial hardships.
    Keywords: Chemistry ; Chemistry ; Fritz Haber Institute ; thema EDItEUR::P Mathematics and Science::PD Science: general issues::PDX History of science
    Language: English
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  • 46
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    transcript Verlag | transcript Verlag
    Publication Date: 2024-04-04
    Description: Die Chemie büßt zugunsten physikalischer und lebenswissenschaftlicher Konzeptionen zunehmend an Deutungsmacht über die molekulare Welt ein. Sandra Lang untersucht, inwiefern die Ausdifferenzierung der chemischen Wissenschaften mit sich ebenfalls ausdifferenzierenden Zugriffen auf das Molekulare zusammenhängt. Anhand der vier exemplarischen Grenzfelder Materialwissenschaften, Biomedizin, Pharmazie und Quantenchemie und deren Narrative zur molekularen Eigenschaft der Chiralität veranschaulicht sie die transformative Phase der Chemie angesichts sich wandelnder Innovationsdispositive.
    Keywords: Chemie ; Chiralität ; Molekülkonzept ; Naturwissenschaften ; Grenzarbeit ; Interdisziplinarität ; Hybridität ; Wissenschaft ; Technik ; Wissenschaftssoziologie ; Techniksoziologie ; Wissenssoziologie ; Wissenschaftsgeschichte ; Soziologie ; Chemistry ; Chirality ; Molecule Concept ; Natural Sciences ; Border Work ; Interdisciplinarity ; Hybridity ; Science ; Technology ; Sociology of Science ; Sociology of Technology ; Sociology of Knowledge ; History of Science ; Sociology ; thema EDItEUR::P Mathematics and Science::PD Science: general issues::PDR Impact of science and technology on society ; thema EDItEUR::J Society and Social Sciences::JH Sociology and anthropology::JHB Sociology
    Language: German
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    De Gruyter | De Gruyter
    Publication Date: 2024-04-11
    Description: Presents technologies and key concepts to produce suitable smart materials and intelligent structures for sensing, information and communication technology, biomedical applications (drug delivery, hyperthermia therapy), self-healing, flexible memories and construction technologies. Novel developments of environmental friendly, cost-effective and scalable production processes are discussed by experts in the field.
    Keywords: Science ; Chemistry ; Industrial & Technical ; Technology & Engineering ; Textiles & Polymers ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TD Industrial chemistry and manufacturing technologies::TDC Industrial chemistry and chemical engineering ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TG Mechanical engineering and materials::TGM Materials science
    Language: English
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    De Gruyter | De Gruyter
    Publication Date: 2024-04-05
    Description: Comprise definition of 1500 terms. Innovation from A to Z presents a glossary, including: Terms, older terms whose meanings have changed, acronyms, synonyms, famous names, selected abbreviations, and cross-references. A highly interdisciplinary approach incorporating strategy and entrepreneurship with technology and engineering sciences, economics, marketing, organizational behavior and theory. Ideal for engineers, managers, sales people and economists. Innovation Technology from A to Z Glossary of terms, including acronyms, synonyms, abbreviations, cross-references 1500 terms supplemented by figures and tables that clearly demonstrate the state-of-the-art in Innovation Technology
    Keywords: Science ; Chemistry ; Technology & Engineering ; Agriculture ; thema EDItEUR::P Mathematics and Science::PN Chemistry ; thema EDItEUR::T Technology, Engineering, Agriculture, Industrial processes::TV Agriculture and farming
    Language: English
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  • 49
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    Coimbra University Press
    Publication Date: 2022-01-31
    Description: This work brings together various contributions from experts in very diverse areas of knowledge, to discuss the theme ‘Light’ from various points of view. The subjects gathered in this work come from the areas of Physics, Philosophy, Transcendence, Chemistry, Optics, Literature, History of Sciences, History, Geography, International Relations, Biology, Psychology, Art, Cinema and Photography, Medicine and Museology. The texts partially reflect the contents presented at the interdisciplinary colloquium ‘Visões da Luz’ held in October 2015, on the occasion of the International Year of Light 2015, under the aegis of III-UC and open to academia and society, to teachers of the Basic and Secondary Education.
    Keywords: Geography ; Chemistry ; Literature ; Geology ; Light ; Optics ; Biology ; History ; Physics
    Language: Portuguese
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    MDPI - Multidisciplinary Digital Publishing Institute
    Publication Date: 2022-01-31
    Description: Today, sustainability of a healthy freshwater ecosystem and its associated ecosystem services are hot issues with ever-growing attention placed upon them. We are increasingly recognizing that they are crucial for the survival of the aquatic biota and human beings on our planet. The efficient monitoring of water resources is fundamental for effective management of water quality and aquatic ecosystems. The first stage in sustainable ecosystem management is the evaluation of the current status of target ecosystems. Traditionally, and even today, physico-chemical parameters have mainly been used to evaluate the quality of water resources. However, they have a large limit to grab the wholeness of water system, particularly in the sense of ecosystem health and integrity, for which ecological monitoring should be based on biological factors. Various approaches are applicable to ecosystem health assessment at different levels of the biological hierarchy, from genes to ecosystems. This Special Issue is designed to improve scientific understanding and strategies for sound aquatic ecosystem management and services for researchers, decision makers, and stakeholders.
    Keywords: Limnology ; Aquatic ecosystem assessment Aquatic ecosystem management ; Restoration ; Aquatic ecosystem services ; Aquatic ecology ; Aquatic ecosystem policy ; Conservation ; Ecohydrology ; Aquatic ecosystem monitoring ; Streams/ Rivers/ Lakes/ Wetlands ; Biological indicators
    Language: English
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 2004-05-29
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Malakoff, David -- New York, N.Y. -- Science. 2004 May 28;304(5675):1283.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/15166364" target="_blank"〉PubMed〈/a〉
    Keywords: Biotechnology ; Career Choice ; Chemistry ; Emigration and Immigration ; History, 20th Century ; History, 21st Century ; Siberia ; United States
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 2003-05-31
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Demaine, Linda J -- Fellmeth, Aaron X -- New York, N.Y. -- Science. 2003 May 30;300(5624):1375-6.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉RAND, Santa Monica, CA 90401, USA. demaine@rand.org〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/12775825" target="_blank"〉PubMed〈/a〉
    Keywords: Aluminum Oxide ; Chemical Phenomena ; Chemistry ; Natural Science Disciplines ; Patents as Topic/*legislation & jurisprudence ; Plant Extracts ; Plant Roots ; Titanium ; United States
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 2002-03-16
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Eisner, Thomas -- Berenbaum, May -- New York, N.Y. -- Science. 2002 Mar 15;295(5562):1973.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/11896239" target="_blank"〉PubMed〈/a〉
    Keywords: Animals ; Biochemical Phenomena ; *Biochemistry ; *Biological Factors/chemistry ; *Biology ; Chemical Phenomena ; Chemistry ; *Ecology ; Ecosystem ; *Molecular Biology ; Research Support as Topic ; United States
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 54
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    In:  J. Geophys. Res., New York, Allerton Press, vol. 106, no. B2, pp. 2221-2234, pp. L13315, (ISSN: 1340-4202)
    Publication Date: 2001
    Keywords: Seismicity ; Geol. aspects ; Israel ; Jordan ; Arabia ; 1035 ; Geochemistry ; (new ; field, ; replaces ; Rock ; Chemistry) ; Geochronology ; 1734 ; History ; of ; geophysics ; Seismology ; 4239 ; Oceanography: ; general ; Limnology ; 7221 ; Paleoseismology ; JGR
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  • 55
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    Accreditation and quality assurance 5 (2000), S. 409-413 
    ISSN: 1432-0517
    Keywords: Key words Metrology ; Comparisons ; Chemistry ; Standards
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract  After stressing the importance in the modern world of accurate and reproducible measurements, the actions taken by the Bureau International des Poids et Mesures to set up, together with the regional metrology organizations, a series of key comparisons are described. They are the technical foundation of a mutual recognition of national measurement standards arrangement prepared in conjunction with the National Metrology Institutes (NMIs). This arrangement also includes the recognition of calibration and measurement certificates issued by these institutes. Then, the consequences of this arrangement for trade are described. The case of chemical analysis is illustrated by the application of the Kyoto protocol on the reduction of greenhouse gases. But the global workload to be taken up by the International Committee of Weights and Measures, its Consultative Committee for Amount of Substance and the NMIs is huge.
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  • 56
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    Earth, moon and planets 88 (2000), S. 35-58 
    ISSN: 1573-0794
    Keywords: Chemistry ; interplanetary dust particles (IDPs) ; Leonids ; meteor trails ; meteoroids ; meteors ; structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The cometary Leonid meteoroids represent a size range in between largest carbon-richIDPs and the smallest CI meteorites. Their dustball structure and chemistry offer anopportunity to constrain hierarchical dust accretion inferred from petrologic studies ofaggregate and cluster IDPs. The Leonid shower meteoroids of known ``comet ejection''ages provide an opportunity to study space weathering of cometary dust over periodsof up to several hundred years. The meteors and aggregate and cluster IDPs displaycontinuous thermal modification of organics and volatile element (Na, K-bearing phases), that occur as discrete minerals and amorphous solids each different response during kinetically controlled ablation. Leonid meteoroids are not excessively Na-rich. The occurrences of Leonid meteors can now be accurate predicted and combined withknowledge better models for the settling rates, collections of surviving dust becomea comet nucleus-sampling mission.
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  • 57
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 801-818 
    ISSN: 1434-1948
    Keywords: Zeolites ; Microporous zeolites ; Titanosilicates ; Transition metal ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stable microporous materials, such as zeolites, are extremely important for applications in catalysis, adsorption, ion-exchange, and separation. In this review we describe a new class of stable microporous materials that involves novel mixed octhaedral-tetrahedral framework oxides. The archetypal material is based on titanosilicates, although there is tremendous scope for introducing many other transition metals. These materials not only have potential novel applications in the fields normally associated with zeolites but also possible applications in the areas of optoelectronics, nonlinear optics, batteries, magnetic materials and sensors.
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  • 58
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 827-830 
    ISSN: 1434-1948
    Keywords: Ammonolysis ; Chlorine ; Nitrogen ; Silicon ; Silsesquiazane ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ammonolysis of trichlorosilanes RSiCl3 [R = CH(SiMe3)2 (1a), Ph (1b), Et (1c)] leads to a series of condensed products such as six-membered rings [(Me3Si)2CHSi(OH)NH]3 (2a) and [PhSi(NH2)NH]3 (2b), disilazane [(Me3Si)2CHSi(NH2)2]2NH (3) and the cage compound (EtSi)6(NH)9 (4). The mixed Si-N-O compound 2a was obtained when liquid ammonia was not dried over sodium prior to use. The reaction with sodium gives NaCl instead of NH4Cl as a by-product which is easily removed by filtration.
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  • 59
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 835-837 
    ISSN: 1434-1948
    Keywords: Gold ; Clusters ; Quantum dots ; Monolayers ; Amphiphiles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Extended ordered monolayers of ligand stabilized Au55 clusters are formed at the phase boundary between water and dichloromethane. The water phase, containing amphiphilic molecules like per-6-deoxy-6-thio-α-cyclodextrin (1) or poly(vinylpyrrolidone) (2), is covered by a thin film of a solution of [Au55(PPh3)12Cl6] in dichloromethane. The interaction of the cluster molecules with the thiol functions of 1 or the polymer chains of 2 form perfect cluster orders of hexagonal and cubic structure. The monolayers can be transferred onto solid substrates by a simple dipping process. The use of carbon coated copper grids allows the investigation of the monolayers by transmission electron microscopy (TEM). Electron diffraction experiments under a microscope prove the hexagonal and cubic arrangements. The reason for the formation of the one or the other modification is still unknown.
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  • 60
    ISSN: 1434-1948
    Keywords: Triosmium cluster ; Biphosphinine ; Crystal structure ; Cyclic voltammetry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structure of the novel cluster [Os3(CO)10(4,4′,5,5′-tetramethyl-2,2′-biphosphinine)] reveals an unprecedented coordination mode of the biphosphinine ligand that occupies a doubly-bridging position spanning the open osmium triangle. The cluster is photostable, pointing to a localization of the lowest-energy electronic transition largely on the negatively charged biphosphinine ligand.
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  • 61
    ISSN: 1434-1948
    Keywords: Photochemistry ; Electrochemistry ; Ruthenium compounds ; α-Diimine complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photophysical, photochemical and redox properties of the title complexes were investigated. Resonance Raman measurements revealed the lowest-energy electronic transition to possess σ→π* character. At low temperatures, long-lived near-IR emission was observed. Irradiation in solution results in homolytic splitting of a Ru-Ru bond as the primary step, followed by secondary reactions of the radical fragments depending on the experimental conditions. (Spectro)electrochemical investigations of the title species proved that the axial [RuCp(CO)2] groups exert a stabilising influence on the corresponding radical cations, while destabilising the corresponding radical anions, compared to the redox behaviour of other ruthenium complexes of this type.
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  • 62
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 889-894 
    ISSN: 1434-1948
    Keywords: Rhodium hydride complexes ; Parahydrogen ; Tin ligands ; Hydrogenations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidative addition of dihydrogen to the [RhH(SnCl3)5]3-/PR3 system (PR3 = PPh3, PEtPh2, PEt3) leads to the formation of previously unknown dihydride complexes, the 1H-NMR spectra of which have been studied by means of the ParaHydrogen Induced Polarization (PHIP) method. The composition of the resulting complexes crucially depends on the type of the added phosphane. With PEt3 as the phosphane and acetonitrile as the solvent, a complex with a SnCl2L ligand (L = CD3CN) can be detected. All systems examined catalyze the hydrogenation of phenylacetylene. During these reactions, both the 1H-NMR resonances of the dihydride complexes and those of styrene, the hydrogenation product of phenylacetylene, can be detected simultaneously. In the case of SnBr3 ligands, hydrogen addition in the presence of phosphanes leads to similar dihydride complexes, which were also identified via 1H-NMR spectroscopy. Furthermore, a mixed complex of the structure [Rh(SnBr3)nBr6-n]3- has been isolated.
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  • 63
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 857-877 
    ISSN: 1434-1948
    Keywords: Crystal packing ; Neural networks ; Pattern recognition ; Organometallic compounds ; Close packing ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structures of hundreds of thousands of molecular compounds have now been determined with the quantitative information being stored in large databases. Chemists are generally interested in that specific part of this information which refers to individual molecules. The packing of molecules and their spatial relation to each other is not the focus of interest, even though the material properties of a molecular crystal are determined by both the packing arrangement of the molecules and their specific properties. The lack of interest in packing has at least one obvious reason. It is difficult for the non-expert to find the appropriate packing categories when looking at a principally infinite lattice. A tool performing this search for individual categories of packing in an automatic manner would therefore be of general importance. The development and application of such a tool is described in this paper. Novel strategies to extract a set of n points forming a specific n-point polyhedron from a set of p points (p 〉 n) is at its basis. Neural networks and second moment analysis are used as the methods of pattern recognition. In order to correlate packing and shape, second moment analysis of molecular shape is also used. This novel method is applied to three classes of organometallic compounds to determine whether the crystals formed by these compounds belong to any of the three classes fcc, bcc, or hcp in an idealized sense. A strong correlation is found between molecular shape and the membership or nonmembership of these classes. The corresponding program, including appropriate tools for visual representation, is available from the authors.
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  • 64
    ISSN: 1434-1948
    Keywords: Arenetricarbonyl chromium complexes ; Palladium ; Cross coupling reaction ; Thiophenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cross coupling reaction of (p-chloroanisole)tricarbonylchromium complex (1) with thiophene derivatives under palladium-catalyzed conditions leads to the selective formation of tricarbonyl-η6-[(2-thiophenyl)arene]- or -η6-[(2-thiophenyl)carbonylarene]chromium complexes (2 or 3) depending on reaction conditions. The conformation of complexes 2 and 3 in the solid state as well as in solution are reported.
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  • 65
    ISSN: 1434-1948
    Keywords: Ruthenium ; Phenanthroline ; Luminescence ; Sterically hindered ligands ; Terpyridine ; Cyclometallation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two series of cyclometallated and noncyclometallated ruthenium(II) complexes incorporating mono- or disubstituted 1,10-phenanthroline- and 2,2′:6′,2′′-terpyridine-type ligands have been synthesized and characterized. An X-ray crystal structure for one of the complexes, Ru(ttpy)(mapH)-(Cl)(PF6), has been obtained (mapH = 2-p-anisyl-1,10-phenanthroline; ttpy = 4′-tolyl-2,2′:6′,2′′-terpyridine). Distinct electrochemical and photophysical properties have been observed for the two series: a remarkable feature is the observation of relatively long-lived MLCT excited states (from 70 to 106 ns at room temperature in CH3CN) for three of the cyclometallated complexes. A discussion is given on the role of factors like sigma donation by the cyclometallating ligands, interligand steric hindrance and interligand π-π interactions that affect the electrochemical and spectroscopic properties.
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  • 66
    ISSN: 1434-1948
    Keywords: Polymeric copper complexes ; Group-subgroup relationships ; 2D-sheets ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and characterisation of two new polymeric CuII complexes is described, i.e. {[Cu(btp)2(CH3CN)(H2O)](CF3SO3)2}n (1) and {[Cu(btp)2(CH3CN)2](ClO4)2}n (2), in which btp = [1,3-bis(1,2,4-triazol-1-yl)propane]. Compound 1 crystallizes in space group P21/c with a = 11.9337(15) Å, b = 20.108(6) Å, c = 12.748(6) Å, β = 92.247(14)°, and Z = 4. Compound 2 crystallizes in space group Pna21 with a = 18.770(8) Å, b = 12.648(8) Å, and c = 12.019(8) Å. The structures refined to R1 values of 0.0683 for 1 and 0.0846 for 2. In both structures the CuII ions are linked by the bridging ligands, resulting in two-dimensional networks. Two such curved layers are arranged on top of each other with center-to-center of layer distances of 2.12 Å in 1 and 1.98 Å in 2. Such double layers are separated from each other by 10.05 Å in 1 and 9.385 Å in 2. The space between the double layers is occupied with interstitial anions. No significant interaction between CuII ions is observed by EPR and magnetic susceptibility measurements. The compounds form a new class of a lattice engineered system held together by the CuII ions. - The coordination geometry of the copper ions is distorted octahedral, with the equatorial plane formed by the N4 nitrogens of the four triazole groups and the axial sites occupied by solvent molecules; acetonitrile and water in structure 1 and two acetonitrile molecules in structure 2. The two structures are related by a group-subgroup relationship, which appears to be the first such case in supramolecular chemistry. - The Cu-N vibrations in the FIR region are found at 274 cm-1 for 1, and at 276 cm-1 for 2. The ligand-field maxima are observed at about 16·103 cm-1, with a shoulder at about 12·103 cm-1. The νCN stretching vibrations of the acetonitrile molecules are found at 2303 and 2261 cm-1 for 1, and at 2313, 2294, 2278, and 2260 cm-1 for 2.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99211_s.pdf or from the author.
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 217-224 
    ISSN: 1434-1948
    Keywords: Reaction mechanisms ; Cyclopalladation ; Acetic acid ; Pd-C bond stability ; Polynuclear species ; Palladium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The processes operating during the synthetic cyclopalladation reactions of imines in acetic acid have been studied from a kinetico-mechanistic point of view. These reactions include a fast initial coordination to the palladium through the N-donor atom of the imine, followed by the proper C-H bond activation to produce the acetato bridged dimeric species. At this point, the lability of the bridging acetato groups, the hydrolysis of the C-Pd bonds, and/or the hydrolysis of C=N exo bonds contribute to the generation of dark red polynuclear compounds. The processes occurring after the C-H activation have been followed kinetically, both from palladium acetate plus imine, and the synthetically pure isolated acetato dimers as starting materials. The kinetic and activation parameters have been found identical within experimental error whatever the starting material was (k323 = 1.5 × 10-4 s-1; ΔH# = 51 kJ mol-1; ΔS# = -163 JK-1 mol-1 ΔV# = +19 cm3 mol-1 for the 4-ClC6H4-CH=N-CH2-C6H5 imine derivative 1a). Acidolysis of C-Pd bonds has been found to occur in these polynuclear species. When alternative monomeric Cbenzylic-Pd bond-containing complexes are possible follow ups of the reactions produce them as final dead-end complexes (k323 = 2.2 × 10-5 s-1; ΔH# = 61 kJ mol-1; ΔS# = JK-1 mol-1 ΔV# ≈ 0 cm3 cm-1 for the [2,4,6-(CH3)3]C6H2-CH=N-CH2-[2-(CH3]C6[H4] imine derivative 3d). The same study has been carried out with primary amines in order to check the validity of the data if C=N bond hydrolysis is taking place in the imine derivatives with exo C=N bonds. For complexes with similar type of metallacycles, the results agree reasonably well with the proposed mechanism [k323 = 1.2·10-4 s-1, ΔH# = 46 kJ·mol-1, ΔS# = -180 J·K-1mol-1, ΔV# = -16 cm3·mol-1 for the polynuclear formation of the C6H5-CH2-NH2 derivative 4e; k323 = 3.0·10-4 s-1, ΔH# = 55 kJ·mol-1, ΔS
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  • 68
    ISSN: 1434-1948
    Keywords: Phosphanylphenolate ; Cyclopentadienylnickel complexes ; Chelates ; Ethylene polymerization ; Crystal structure ; Polymerizations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Diphenylphosphanyl- and 2-alkylphenylphosphanyl-4-methylphenols 1 or their silyl ethers 2 and equimolar amounts of nickelocene react in benzene preferably to give orange-brown diamagnetic cyclopentadienylnickel chelate complexes [η-CpNi(P∩O)] (3). Addition of a second equivalent of 1 or 2 affords (RR) and (SS) diastereoisomers of cis-bis(P∩O-chelates) 4a-c (R = Ph, Me, iPr) or the unsymmetrical cis-bis(P∩O-chelate) 5, whereas with bulkier substituted derivatives 1d or 2d (R = tBu) the second step is hindered or retarded. The reactivity of 1d remains high towards nickel salts in polar solvents, but in contrast to 1a-c, yielding 4, a sparingly soluble green trans-bis(P-O-chelate) nickel complex 6d is formed. Complexes formed in situ from 1 or 2 and Ni(COD)2 in toluene catalyze the polymerization of ethylene. The cyclopentadienyl (P∩O) complexes 3, however, are too stable to be active in this process. The crystal and molecular structure of 3c and 4c are described.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99035_s.pdf or from the author.
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  • 69
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 287-297 
    ISSN: 1434-1948
    Keywords: Enolates ; Nucleophilic additions ; Ruthenium ; S ligands ; Sulfenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of the chiral racemic complex [CpRu(mppe)(SO2)]PF6 (1, mppe = Me2PC2H4PPh2) with diazomethane or -ethane gave the sulfene complexes [CpRu(mppe)(RHC/SO2)]PF6 (R = H, 2a; R = Me, 2b). Treatment of 2a with prochiral enamines or deprotonated β-oxo esters yielded C-C coupling products with 32-60% de. An analog of 2a, [NmcpRu(mppe)(H2C/SO2)]PF6 (8, Nmcp = neomenthylcyclopentadienyl) was prepared in a four-step synthesis starting from LiNmcp and [RuCl2(PPh3)3]. Repeated crystallization of the intermediate [NmcpRu(mppe)Cl] (6) provided diastereomerically pure 6′ which added methylene stereospecifically to give diastereomerically pure 8′. Compound 8 turned out to be much less reactive towards nucleophiles than 2a, but still added deprotonated ethyl 2-methyl-3-oxobutanoate with 44% de. The chiral, enantiomerically pure sulfur dioxide complex [CpRu(chir)(SO2)]PF6 [10, chir = (S,S)-Ph2PCHMeCHMePPh2] was synthesized from [CpRu(chir)Cl] and SO2 and was characterized by X-ray crystallography. Reaction of 10 with diazomethane gave the enantiomerically pure sulfene complex [CpRu(chir)(H2C/SO2)]PF6 (11). Addition reactions of 11 with N-(1-cyclopentenyl)morpholine, as well as with various enolates derived from β-oxo esters or 1,3-diesters proceeded with high yields and 20-90% de. The structure of a diastereomerically pure addition product, [CpRu(chir)(SO2CH2C(Me){C(O)Me}{C(O)OtBu}] (13d′), was determined crystallographically and was shown to have (R) configuration at the quaternary carbon atom. After alkylation of one of the S/O functions, the sulfinate ligand was cleaved from the metal center by ligand substitution with acetonitrile, and the resulting acetonitrile complex 15 was converted back into 10 by treatment with SO2.
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  • 70
    ISSN: 1434-1948
    Keywords: Metal-rich antimonides ; Magnetism ; Structure and bonding ; Conductivity ; LMTO ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title compounds can be synthesized in quantitative yields by arc-melting of stoichiometric amounts of HfSb2, Hf and one of the 3d metals V, Cr, Mn, Fe, Co, Ni, and Cu. These antimonides crystallize in a substitution variant of the W5Si3 type, in which one position is statistically mixed, occupied by the 3d metal atom M or the Sb2 atom in different ratios. Within the linear (M,Sb) chain, the M:Sb ratio may vary between 3:1 and 2:3. According to calculations of the electronic structures of Hf10MδSb6-δ with δ = 1, these phases are metallic compounds stabilized by strong Hf-Hf, Hf-M, and Hf-Sb bonds, and to a smaller extent by bonding interactions within the linear (M,Sb) chain. The metallic character was confirmed by measurements of the electrical resistivity and the magnetism of selected samples. Whereas Pauli paramagnetism was observed experimentally for M = V, Co, and Ni, Hf10FeSb5 is apparently the only phase with localized magnetic moments and magnetic coupling. This is in agreement with the magnetic ground state obtained solely for the ordered structure model of Hf10FeSb5 with spin-polarized calculation within the local spin density approximation.
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 323-330 
    ISSN: 1434-1948
    Keywords: Amino acids ; Alkynes ; Ferrocene ; Palladium ; Catalysis ; Bioorganometallic chemistry ; Biosensors ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This work describes a Pd-catalyzed coupling of ferrocene alkyne derivatives to iodo amino acids. Ferrocene carboxylic acid propargyl amides were easily obtained in high yield. The crystal structures of the propargyl amine derivative 3 and the 1,1-diethylpropargylamine derivative 4 have been determined by X-ray diffraction. Pd-catalyzed coupling to p-iodoanilide amino acids gave the corresponding ferrocene-labeled amino acid derivatives, which were easily purified by diethyl ether extraction in the case of the 1,1-diethyl derivatives 8. The coupling reaction did not require anhydrous solvents and tolerated a variety of functional groups present in peptides such as alcohols (8a, Ser), thioethers (8d, Met), disulfide bonds (cystine, 12) esters (as in the N-labeled Leu derivative 10) and of course amides. A minor by-product of the coupling reaction, namely the homo-dimer bis(ferrocene carboxylic acid propargylamide) 9, was identified in the crude reaction mixtures by mass spectrometry and independently synthesized by oxidative coupling (Glaser and Eglington) of 3. All new compounds were completely characterized spectroscopically, including 15N- and 2D NMR spectroscopy, Mössbauer spectroscopy and electrochemistry. This work introduces a versatile procedure for a selective functionalization of amino acids with organometallics at the C-terminus which is expected to be of general applicability to peptide chemistry.
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  • 72
    ISSN: 1434-1948
    Keywords: Palladium ; Insertion reactions ; Tridentate ligands ; Hydrazones ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Potentially tridentate hydrazonic ligands of the type HNNO have been used in the synthesis of some methyl palladium(II) complexes. Depending on the applied experimental conditions two different kinds of complexes are obtained. Thus, the reactions between HL1-HL5 and (COD)PdMeCl in diethyl ether led to the formation of bidentate methyl complexes of the type Pd(HNN)MeCl (1-5), where the ligands maintain a neutral character. However, in the presence of a base such as Et3N or NaOMe, the ligands are deprotonated with the consequent formation of tridentate methyl complexes of the type Pd(NNO)Me (7-10). In solution, complexes 1-5 tend to lose the hydrazonic proton with elimination of methane and formation of a tridentate chloride complex Pd(NNO)Cl (6); this tendency can be correlated with the acidity of the free ligands, which has been determined. On bubbling carbon monoxide through solutions of 1-5, the corresponding acetyl complexes Pd(HNN)[C(O)Me]Cl (11-15) are formed, in which both the cis and trans isomers are present. Their molar ratio is rationalised from the results of a molecular modelling study on the basis of electronic considerations. A remarkably different reactivity has been found in the carbonylation of the tridentate complexes 7-10: they decompose rapidly and quantitatively to palladium black and an organic product corresponding to the ligand with an acetyl group bonded to the hydrazonic nitrogen. The X-ray structures of a methyl complex (3) and its corresponding acetyl (13) derivative have been determined.
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  • 73
    ISSN: 1434-1948
    Keywords: Vanadyl arsenate ; Hydrates ; Layered compounds ; Vibrational spectroscopy ; X-ray scattering ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The course of the intercalation and deintercalation of water molecules in vanadyl arsenate has been studied by X-ray diffraction analysis and by infrared and Raman spectroscopies. The formation of VOAsO4 hydrates at ambient temperature has been found to depend on relative humidity (r.h.): VOAsO4 · 5 H2O (basal spacing c = 10.48 Å) is formed at r.h. above 76%, VOAsO4 · 3 H2O (c = 8.03 Å) at 43-76% r.h., VOAsO4 · 2 H2O (c = 7.33 Å) at 11-43% r.h.; dehydrated VOAsO4 (c = 4.18 Å) exists near 0% r.h. Like the thermal dehydration of VOPO4 · 2 H2O, the thermal dehydration of VOAsO4 · 3 H2O proceeds in a stepwise manner so that the dihydrate and monohydrate are formed en route to the anhydrous compound. The arsenate monohydrate is gradually dehydrated over a broad temperature range. The broad diffraction lines observed can be explained in terms of the existence of a disordered phase containing monohydrated and anhydrous forms of vanadyl arsenate. A similar phenomenon has been observed during the dehydration of VOAsO4 · 3 H2O over phosphorus pentoxide at ambient temperature. The hydration of VOAsO4 is different from that of VOPO4. The first step, i.e. the insertion of water that coordinates to the vanadium atoms, is very slow. On the contrary, the uptake of further water molecules with the formation of higher hydrates is fast. It thus seems likely that the filling of one interlayer space with water facilitates the intercalation of further water into neighboring interlayer spaces. Therefore, only higher hydrates together with the original anhydrous phase are observed. Impedance spectral measurements indicate that the conductivity of the trihydrate has a mixed ionic/electronic character.
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  • 74
    ISSN: 1434-1948
    Keywords: Coordination chemistry ; α-Imino ketones ; CO complexes ; Iron complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of Fe2(CO)9 at room temperature in THF or toluene with the α-imino ketones R1N=C(R2)-C(R3)=O (L) (R1 = alkyl, R2 = H, Me, Ph, R3 = Me, Ph) (a-k), initially results in the formation of the mononuclear chelate Fe(CO)3(α-imino ketone) complexes 6 which can be isolated in moderate (6h) to high (6e-g) yield. Under these reaction conditions, complexes 6 subsequently react with [Fe(CO)4] fragments or dimerise, to form the dinuclear complexes Fe2(CO)6(α-imino ketone) (7a-j) or Fe2(CO)4(L-L) (8a,b,k), respectively. The complexes 8 contain two α-imino ketone ligands C-C coupled at the ketone carbon atoms. Complexes 8a,b react with CO at elevated temperatures to quantitatively yield Fe(CO)3(α-imino ketone) (6a,b). This reaction can be reversed photochemically. Irradiation of a solution of 6a,b in the low-energy band results in the reformation of 8a,b in almost quantitative yield. The extremely air-sensitive complexes 6 and the dinuclear complexes 7 and 8 have been characterised spectroscopically (IR, UV/Vis, 1H and 13C NMR) and by elemental analysis. The solid state structures of complexes 6g and 8a have been determined by single-crystal X-ray diffraction. The molecular structure of 6g confirms the flat σ-O,σ-N chelate coordination of the α-imino ketone. The structure of 8a consists of two metal-metal-bonded Fe(CO)2 units, bridged by a formally 10e-donating dianionic C-C coupled (tBu-ADO) ligand. A mechanism for the formation of complexes 8 is discussed.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99351_s.pdf or from the author.
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  • 75
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 929-932 
    ISSN: 1434-1948
    Keywords: Titanium ; Cyclopentadienes ; Arene complexes ; Cations ; Bridging ligands ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The half-sandwich titanium trimethyl complex (η5-C5H4CMe2Ar)TiMe3 (Ar = 3,5-Me2C6H3) reacts with the Lewis acid B(C6F5)3 to give the ionic TiIV ansa-cyclopentadienyl-arene complex [(η5,η6-C5H4CMe2Ar)TiMe2][MeB(C6F5)3]. In bromobenzene solvent, addition of more B(C6F5)3 leads to C6F5/Me exchange and, subsequently, to formation of an unusual dimeric TiIII dicationic species, {[(η5,η6-C5H4CMe2Ar)Ti(μ-Br)]2}[B(C6F5)4]2, which was structurally characterized. Its formation involves reduction of the transition-metal center, solvent C-Br cleavage and perfluoroaryl-group scrambling.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99383_s.pdf or from the author.
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  • 76
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    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 939-941 
    ISSN: 1434-1948
    Keywords: Germanium ; Germanol ; Hydrogen bonds ; X-ray structure ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hydrolysis of tBu2Ge(OEt)2 is described. Depending on the amount of water used either tBu2Ge(OH)2 (1) or a mixture of the latter and (tBu2GeOH)2O (2) were obtained. A cocrystallate consisting of 2tBu2Ge(OH)2, (tBu2GeOH)2O and water was the subject of a single crystal X-ray diffraction study. In the solid state the individual molecules are connected by hydrogen bonds giving rise to the formation of a polymeric double chain ribbon.
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  • 77
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 959-969 
    ISSN: 1434-1948
    Keywords: Bipyridyldiphosphane ligands ; Macrocycles ; Metallacyclophanes ; Platinum ; Supramolecular chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 5,5′-bis(hydroxyalkyl)-2,2′-bipyridines 4a-c (Scheme 1) were prepared either in one step (4b, 4c) or in four steps (4a) starting with 5,5′-dimethyl-2,2′-bipyridine in each case. Reaction of 4a-c with mesyl chloride afforded the bis(mesylates) [-C5H3N-(CH2)n-CH2-OSO2Me]2 5a-c [n = 1 (a), 2 (b), 3 (c)], which could easily be transformed into the diphosphanes 6a-c by reaction with LiPPh2. Treatment of 6c, 6b with Cl2Pt(NCPh)2 and (RC6H4)2Pt(COD) according to the high-dilution method resulted in the formation of the tetraphosphadiplatinacyclophanes [-C5H3N-(CH2)4-PPh2PtCl2PPh2-(CH2)4-C5H3N-]2 (7c) and [-C5H3N-(CH2)3-PPh2Pt(C6H4R)2PPh2-(CH2)3-C5H3N-]2 (8b, 9b) (8b: R = H, 9b: R = tBu), respectively (Scheme 2). The molecular structures of 8b and 9b were elucidated by X-ray structural analyses. The noncoordinated bipyridine moieties in 8b were employed to encapsulate copper(I) to give the host/guest complex 10b (Scheme 3), which was investigated by FAB-MS, NMR spectroscopy, and cyclovoltammetry. 10b exhibited a quasi-reversible oxidation at E1/2 = -0.31 V and an electrodeposition-redissolution redox system at E1/2 = -0.79 V, owing to the formation of copper at the surface of the working electrode.
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  • 78
    ISSN: 1434-1948
    Keywords: Lanthanides ; Ytterbium ; MRI contrast agents ; Solid-state structures ; Hydration ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The low temperature (-100 °C) X-ray structure of the complex K2[Yb(DTPA)(H2O)] has been determined. The metal ion is at the center of a tricapped trigonal prism and is nine-coordinate, binding to the three nitrogens and five oxygens of the ligand and one water molecule. From the structure obtained, three well-defined hydration shells can be observed consisting of: i) one coordinated water molecule; ii) several water molecules in the outer coordination sphere of the YbIII ion and iii) one water molecule surprisingly close to the metal center and hydrogen-bonded to proximate carboxylate groups. A variable-field and temperature NMRD study of the corresponding Gd complex has been performed and the data interpreted by taking into account the presence of second-sphere water molecule(s). The results of the analysis are in excellent agreement with the X-ray structural data.
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  • 79
    ISSN: 1434-1948
    Keywords: Catalysis ; Densitiy functional theory ; Epoxidation ; Reaction mechanisms ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Seven-coordinated molybdenum oxobisperoxo complexes with chelate nitrogen donors like pyrazolylpyridines are catalysts for the epoxidation of olefins. An NMR spectroscopic and quantumchemical study on the fluxionality of the chelate ligand proves that during this process partial ligand dissociation takes place. This gave rise to a detailed theoretical study on the activation of CH3OOH at the model complex (NH3)2MoO(O2)2 including dissociation of one of the ammonia ligands and proton transfer from the hydroperoxide to one of the peroxo ligands.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99429_s.pdf or from the author.
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  • 80
    ISSN: 1434-1948
    Keywords: Palladium ; Tripodal ligands ; O ligands ; Fluxionality ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of [PdCl2(CH3CN)2] with the silver salt of the tripodal oxygen ligand L- = [(C5H5)Co{P(O)(OMe)2)}3]- yields the homoleptic oxygen ligand complex [PdL2] (1). The molecular structure of 1 was determined by single-crystal X-ray diffraction: monoclinic space group P21/n; a = 8.515(1), b = 13.627(2), c = 15.828(2) Å; β = 92.44(1)°; V = 1834.9(7) Å3; Z = 2. The complexes [Pd(PPh3)XL] [X = Cl (2a), Br (2b), I (2c)] have been prepared starting from 1. Complex 2a reacts with PPh3 to form [Pd(PPh3)2L]Cl (3a) and [Pd(PPh3)2L]L (3b). Treatment of 2a with CO in MeOH yields the carboxymethyl complex [{(PPh3)(COOMe)Pd(μ-Cl)}2] (4) and the protonated ligand HL. The carboxymethyl complex 4 shows some catalytic activity for the copolymerization of CO and ethene. Complex 4 reacts with AgL to yield [Pd(PPh3)(COOMe)L] (6). Alkylation of 2a with Me4Sn leads to the methyl complexes [Pd(PPh3)MeL] (7) and [Me2ClSnL] (8). CO insertion in the palladium-carbon bond of 7 gives the stable acetyl complex [Pd(PPh3){C(O)Me}L] (10). The palladium(II) complexes 1, 2, 3, 6, 7, and 10 of the tripodal oxygen ligand L are all fluxional molecules that have been studied by temperature-dependent 1H- and 31P-NMR spectroscopy.
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  • 81
    ISSN: 1434-1948
    Keywords: Tripod ligands ; Hindered rotation of vinylidene ligands ; CpML2 chelate ligands ; Ruthenium ; Carbenes ; Carbene-type ligands ; Cyclic voltammetry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tripodal ligand [CH3C(CH2C5H4)(CH2PPh2)2]- reacts with RuCl2(PPh3)3 to produce CH3C(CH2-η5-C5H4)(CH2-η1-PPh2)2RuCl, [tripodCpL2RuCl], 1. Complex 1 undergoes substitution of the chlorine function with various nucleophiles L′ to produce [tripodCpL2RuL′]+. The carbonyl derivative (L′ = CO) 2, isonitrile (L′ = RNC) 3, nitrile compounds (L′ = RCN) 4, and a tolane adduct (L′ = η2-PhC≡CPh) 5 are obtained when 1 is treated with the appropriate ligands in polar solvents. Halide acceptors (e.g. TlPF6) are generally needed to promote these reactions. The cyanide derivative tripodCpL2RuCN (3a) is alkylated by F3CSO3CH3 to give the isonitrile derivative [tripodCpL2RuCNMe]+3b. Terminal alkynes HC≡CR produce vinylidene compounds [tripodCpL2RuL′]+, where L′ = C=CHR (R = tBu, 7b; R = Ph, 7c), or allenylidene derivatives, L′ = C=C=CPh2 (6), depending on the nature of R (R = CPh2OH for synthesis of 6). Trimethylsilylacetylene gives the parent vinylidene species, L′ = C=CH2 (7a), which is transformed to the Fischer-type carbene compound, L′ = C(OMe)Me (8), upon treatment with methanol. The vinylidene species 7 are deprotonated by NaOMe to produce the alkynyl compounds tripodCpL2RuC≡CR (9). Methylation of 9 with F3CSO3CH3 results in the vinylidene derivatives L′ = C=C(Me)R (R = tBu, 7d; R = Ph, 7e), having two organic substituents at the terminal carbon centre. For all vinylidene compounds with two different substituents at their terminal carbon atom, hindered rotation of the single-faced vinylidene π-ligand about its Ru-C bond is observed. Analysis by 31P-NMR spectroscopic coalescence measurements as well as line-shape analyses reveals activation enthalpies of around 40 kJmol-1 for this rotation, with small activation entropies of around ±10 Jmol-1K-1. Solid-state structures of nine compounds of the type [tripodCpL2RuL′]+n (n = 0, 1) demonstrate the remarkable conformational rigidity of the tripodCpL2Ru template. They also show that the possible strain imposed by linking the Cp ligand and the two donor groups L in one and the same chelate scaffolding does not appear to impose a serious steric strain on these templates.
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  • 82
    ISSN: 1434-1948
    Keywords: (R)-(+)-2,3-Epoxy-1-propanol ; 2,3-Dihydroxyalkyl phosphanes ; 1,3,2-Dioxaborolane ; 1,3-Dioxolane ring ; Enantiopure phosphanes ; Complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of (R)-(+)-2,3-epoxy-1-propanol with Ph2PH, Ph(Me)PH, or PhPH2 in the superbasic medium KOH/DMSO affords the novel chiral phosphanes 1a-1c. While 1a is obtained enantiomerically pure, 1b and the secondary phosphane 1c are formed as mixtures of diastereoisomers (RPRC, SPRC) with homochiral β carbon atoms. Derivatization of 1a with phenylboronic acid or 2,2-dimethoxypropane yields 2a and 3a with 1,3,2-dioxaborolane and 1,3-dioxolane ring systems, respectively. The X-ray structure of 2a (space group P21) reveals the presence of four molecules of R configuration in the unit cell. Nucleophilic phosphanylation of (R)-(-)-2,3-O-isopropylideneglycerol tosylate with Ph2PH, Ph(Me)PH, or PhPH2 yields chiral 3a-3d. Compound 3b was obtained enantiomerically pure. The secondary phosphane 3c has been employed in syntheses of the hydrophilic tertiary phosphanes 3e, 3f and of the novel bidentate phosphane ligands 3g, 3h, all of which have homochiral β carbon atoms. PdII complexes PdL2Cl2 of 1a, 2a, 3a (L) are formed as mixtures of cis/trans isomers. RhI complexes of 1a, 3a, and bidentate 3h have also been synthesized.
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  • 83
    ISSN: 1434-1948
    Keywords: Macrocycles ; Nickel ; Redox chemistry ; Schiff bases ; S ligands ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A single crystal X-ray analysis of [Ni2L1](ClO4)2· MeCN · 1/4 H2O, 1a [formed directly from a mixture of nickel(II) template ions, 2,6-diformyl-4-methyl-thiophenolate, and 1,4-diaminobutane] reveals that the nickel(II) ions are in square-planar N2S2 environments and that the four “bowed” dinickel macrocycles in the asymmetric unit pack around a single central perchlorate template ion encapsulating it to form “star” clusters of stoichiometry {[Ni2L1]4(ClO4)}7+. These “stars” stack together, via π-π-stacking interactions, to form two-dimensional sheets, which are separated from one another by layers of the remaining perchlorate anions and solvent molecules. Reduction, by NaBH4, of the four imine bonds in [Ni2L2](ClO4)22a (analogous to 1a but formed from 1,3-diaminopropane not 1,4-diaminobutane) or [Ni2L2](CF3SO3)22b to amine bonds produces the corresponding tetra-amine complex, [Ni2L3](ClO4)23. These complexes are shown to contain diamagnetic nickel(II) ions by a combination of magnetic, NMR and UV/Vis spectroscopic results. The 1H NMR spectra of 1-3 run in [D3]MeNO2 and in [D3]MeCN are consistent with increasing axial binding ability in the order: 3 〈 2 〈 1. Thiocyanate ion binding studies reveal that 1 and 2 are able to coordinate two thiocyanate ions, forming [Ni2L1(NCS)2] 4 and [Ni2L2(NCS)2] 5 respectively, whereas 3 does not. Single crystal X-ray analyses of complexes 4· 2 MeCN and 5· MeCN show that adjacent square-planar and octahedral nickel(II) ions result. Two one-electron oxidations and two one-electron reductions are a feature of the electrochemistry of 1-3 in MeCN: curiously, the potentials for the oxidation processes are almost invariant whereas those for the reduction processes vary as anticipated. EPR spectroscopy shows that the first one-electron reduction process and the first one-electron oxidation process are metal centred. Spectroelectrochemical studies and redox titrations indicate that a purplish-coloured complex is produced by one-electron oxidation of 2 (λ = 870 nm, ε = 1320 L mol cm-1). The synthesis of a phenolate analogue, [Ni2L′(MeCN)4](ClO4)2 (6), of the thiophenolate complex 2a is also detailed. Complex 6 undergoes two one-electron oxidations in MeCN, but, in contrast to the thiophenolate complexes 1-3, these occur at much higher potentials. Only a single one-electron reduction process is observed and this occurs at a more negative potential than for any of 1-3.
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  • 84
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 195-203 
    ISSN: 1434-1948
    Keywords: Acid derivatives ; Cyclen and cyclam derivatives ; Phosphinic acid ; Potentiometry ; Protonation and stability constants ; 31P-NMR titration ; Hydrogen bonding ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two phenylphosphinic acid derivatives of tetraaza macrocycles, (1,4,7,10-tetraazacyclododecanetetrayl)tetrakis(methylene)tetrakis(phenylphosphinic acid) [(H4L1) and (1,4,8,11-tetraazacyclotetradecanetetrayl)tetrakis(methylene)tetrakis(phenylphosphinic acid)] (H4L2), were synthesised and the crystal structures of H4L2 and its bis(1-adamantylammonium) salt were determined. In both the structures, the ring conformation is virtually the same and is stabilised by hydrogen bonds. Protonation constants of the acids and stability constants of their Zn2+ and Cd2+ complexes were determined pH-metrically at 25 °C and at an ionic strength of 0.1 mol dm-3 (KNO3). The pKA values found for both the compounds are lower than those for their carboxylic analogues and correspond to the expected electron-withdrawing ability of the -P(Ph)O2H moiety. The value pK1 of the last dissociation constant of H4L1 is surprisingly high. The complexes of Zn2+ and Cd2+ with (L1)4- and (L2)4- are less stable than those with other similar ligands, which is in accordance with lower overall basicity of H4L1 and H4L2. A pronounced drop in the stability of the complexes of H4L2 can be explained by partial coordination of the ligand to the metal ions. The solution properties of the ligands were also investigated by 31P-NMR spectroscopy. The spectra observed suggest stable (on the NMR time scale) conformations of the protonated ligands in solution. A comparison of NMR spectra in solution and CP/MAS-NMR spectra indicates that the structures of the conformers roughly correspond to the structures observed in the solid state. The conformations are stabilised by intramolecular hydrogen bonds and by hydrophobic interactions of phenylphosphinic moieties. The conformers are stable even at 90 °C, but not in the presence of complexing metal ions.Supporting information for this article is available on the WWW under -//_/_http://www.wiley-vch.de/contents/jc_2005/2000/99149_s.pdf or from the author.
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  • 85
    ISSN: 1434-1948
    Keywords: Rare earth complexes ; Naphthalocyaninato ligand ; Double-decker complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of rare earth(III) double-deckers RE[Nc(tBu)4]2 [RE = La, Ce, Pr, Nd, Eu, Gd, Tb, Y, Er; Nc(tBu)4 = dianion of tetra(tert-butyl)-2,3-naphthalocyanine] (1-9) have been prepared by treating RE(acac)3·n H2O (acac = acetylacetonate) with 6-tert-butylnaphthalonitrile in refluxing n-octanol in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). These novel sandwich-type complexes have been spectroscopically characterized. The electrochemical studies show that the first oxidation and the first reduction potentials increase with the size of the central metal ions with a relatively small separation (0.28-0.33 V), reflecting the narrow HOMO-LUMO gap.
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  • 86
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    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 229-239 
    ISSN: 1434-1948
    Keywords: Pyridine derivatives ; Bipyridine derivatives/Metal complexes ; Chromophores ; Nonlinear optics ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metal complexes of pyridine and bipyridine-type ligands represent an important class of nonlinear optical (NLO) materials: (i) They can incorporate a variety of functionalised ligands with a wide range of metals which can give rise to tuneable NLO properties; (ii) they are generally associated with intense low-lying charge-transfer excitations such as metal to ligand charge-transfer (MLCT) or intraligand charge-transfer (ILCT); (iii) bipyridyl ligands are also good building blocks that allow the construction of octupolar complexes with a defined geometry and symmetry. This review describes the recent developments in the design of such dipolar and octupolar chromophores for second-order nonlinear optics.
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  • 87
    ISSN: 1434-1948
    Keywords: Heterobimetallics ; Hydride complexes ; Alkenyl complexes ; μ-Isonitrile complexes ; Silicon ; Iron ; Platinum ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The heterobimetallic hydride complexes [(OC)3Fe{Si(OMe)3}(μ-Ph2PXPPh2)Pt(H)(PR3)] (1a: X = CH2, PR3 = PPh3; 1b: X = NH, PR3 = PPh3; 1c: X = CH2, PR3 = PMePh2) have been prepared by the oxidative addition of [(OC)3Fe(H){Si(OMe)3}(η1-Ph2PXPPh2)] to [Pt(H2C=CH2)(PPh3)2] or by reaction of K[(OC)3Fe{Si(OMe)3}(η1-dppm)] with trans-[Pt(Cl)(H)(PPh3)2]. The solid-state structure of compound 1b has been determined by single-crystal X-ray diffraction. 1-Alkynes such as methylpropiolate or phenylacetylene insert in a regiospecific manner into the Pt-H bond of 1 to yield the σ-alkenyl complexes [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-Ph2PXPPh2)Pt{C(R)=CH2}] (2a: X = CH2, R = CO2Me; 2b: X = NH, R = CO2Me; 3a: X = CH2, R = Ph). Addition of the Pt-H bond of 3a across the triple bond of [D1]phenylacetylene affords [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppm)Pt{C(Ph)=C(D)H}] (3a*) having the deuteron trans to platinum (cis addition). This insertion reaction is accompanied by dissociation of the platinum-bonded PR3 ligand and saturation of the vacant coordination site by a dative μ-η2-Si-O→Pt interaction. When 3 is treated with PR3 again, a subsequent phosphane-induced rearrangement leading to vinylidene-bridged complexes [(OC)3Fe{μ-C=C(H)R′}(μ-Ph2PXPPh2)Pt(PR3)] (4a: X = CH2, R′ = Ph, PR3 = PPh3; 4b: X = NH, R′ = Ph, PR3 = PPh3; 4c: X = CH2, R′ = Ph, PR3 = PMePh2; 4d: X = CH2, R′ = p-tolyl, PR3 = PPh3) occurs. Upon purging a solution of 3a with carbon monoxide, the labile CO adduct [(OC)3Fe{Si(OMe)3}(μ-dppm)-Pt(CO){C(Ph)=CH2}] 5a is formed, addition of 2,6-xylyl isocyanide to 2a and 3a affords the isonitrile adducts [(OC)3Fe{Si(OMe)3}(μ-dppm)Pt(CNxylyl){C(R)=CH2}] (5b: R = CO2Me; 5c: R = Ph), respectively. When hydride complex 1a is allowed to react with stoichiometric amounts of aromatic isonitriles, formal elimination of HSi(OMe)3 occurs, yielding the heterodinuclear isonitrile-bridged complexes [(OC)3Fe(μ-C=N-R)(μ-dppm)Pt(PPh3)] (6a: R = 2,6-xylyl; 6b: R = o-anisyl; 6c: R = p-anisyl; 6d: R = p-C6H4NH2) and the bis(isonitrile) complexes [(OC)2(RN≡C)Fe(μ-C=N-R)(μ-dppm)Pt(PPh3)] (7a: R = 2,6-xylyl; 7b: R = p-anisyl). Single-crystal X-ray diffraction studies perfomed on 6a and 6b reveal that the molecular structures of these μ-isonitrile complexes closely resemble the μ-vinylidene complexes 4. The two metal centers are bridged in a symmetric manner by strongly bent CNR ligands, the aromatic groups R being oriented towards the Fe(CO)3 moiety. Electrophilic addition of HBF4 to the basic nitrogen atom of the μ-CNR ligand transforms 6 to the cationic μ-aminocarbyne complexes [(OC)3Fe{μ-CN(H)R}(μ-dppm)Pt(PPh3)][BF4] (8a: R = 2,6-xylyl; 8b: R = p-anisyl; 8c: R = p-C6H4NH2).
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  • 88
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 253-264 
    ISSN: 1434-1948
    Keywords: Iron-sulfur clusters ; Crown ethers ; Electrochemical devices ; Host-guest chemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of Fe4S4 cluster compounds, I, III, and V, in which the cuboidal cluster core is appended with four crown ether thiolate ligands, and II and IV, bearing thiolate ligands without crown ether parts, has been synthesized and characterized. The spectroscopic and electrochemical properties of these compounds are determined by the electronic nature of the thiolate ligands. Only in the case of III, where a very short α-thioacetyl linker was used to connect the crown ether ligands to the cluster core, was a restricted conformational freedom of the ligand observed. A detailed electrochemical study of the influence of alkali and earth alkali metal ions (Li+, Na+, K+, Mg2+, and Ba2+) on the reversible 2-/3- reduction of the cluster compounds was performed. In the case of the crown ether appended clusters I, III, and V, the addition of these metal ions resulted in an anodic shift, i.e. in positive direction, of the reduction potential (modulation effect) and to larger current responses (promotion effect). The magnitude of the modulation effects is determined by the binding affinity of the metal ions in the crown ether ligands, and by the distance between bound metal ions and the redox active cluster core. Variation of the linker between the cluster core and the metal ion binding site resulted in cluster compounds with almost inverse selectivities for e.g. K+ and Ba2+ in the case of I and III. For the large effects found for compound I a lariat binding mode is proposed.
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  • 89
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 281-285 
    ISSN: 1434-1948
    Keywords: NMR spectroscopy ; Zeolites ; Al-coordination ; Mordenite ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 27Al 3Q MAS NMR spectroscopy has been applied to study the coordination state of the species giving the 30 ppm Al NMR signal in the 27Al MAS NMR spectrum of activated mordenite materials. From the 27Al 3Q MAS NMR measurements it is evident that the broad peak at 30 ppm in the 27Al NMR spectrum of the mordenite calcined at temperatures up to 600 °C comes mainly from the distorted four-coordinated Al. By simulation a quadrupolar coupling constant of 5.8 MHz was estimated for the distorted tetrahedral Al. For samples calcined at 650 and 700 °C, a small amount of pentacoordinated Al emerges. The majority of the signal, however, arises from distorted tetrahedral Al. A two-step calcination results in a significant contribution of the pentacoordinated Al to the signal at 30 ppm. From the simulated line-shape, a quadrupole coupling constant of 6.2 MHz is obtained for the latter signal. These data show that during the calcination of the mordenite, the coordination environment at the Al centre gradually becomes distorted to give rise to the shoulder at 30 ppm. With the increase of the calcination temperature, pentacoordinated Al species form
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  • 90
    ISSN: 1434-1948
    Keywords: Copper ; Magnetic properties ; Supramolecular chemistry ; Three-dimensional architecture ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel three-dimensional copper(II) compound of the formula [Cu3(btre)5(H2O)2](ClO4)6·H2O (btre = 1,2-bis(1,2,4-triazol-4-yl)ethane) has been synthesized. The structure has been solved at 150 K by single-crystal X-ray analysis. The compound [C30H44Cu3N30O2·6(ClO4)·H2O] crystallizes in the triclinic space group P1bar with a = 12.488(1), b = 13.195(1), c = 19.756(2) Å, α = 78.959(8), β = 84.553(8), γ = 63.869(7)°, V = 2868.4(5) Å3, Z = 2 (trinuclear CuII units), 6484 reflections [I 〉 4σ(Ι)], RF = 0.0581, wR2 = 0.1214. The structure of this coordination polymer consists of a three-dimensional network built up from linear trinuclear CuII cations of formula [Cu3(btre)5(H2O)2]6+. This crystallographically independent unit comprises a linear array of three CuII ions linked by triple N1,N2-1,2,4-triazole bridges, yielding Cu1-Cu2 = 3.893(1) Å and Cu2-Cu3 = 3.889(1) Å. These linear trinuclear CuII units are linked by various pathways involving tridentate and tetradentate bridging btre ligands, which yields an unprecedented three-dimensional network. The CuII ions are weakly antiferromagnetically coupled with J = -1.01(2) cm-1 (based on the Hamiltonian: H = -J[SCu1·SCu2 + SCu2·SCu3] using the expression for the molar magnetic susceptibility S = 1/2 of a linear trinuclear system). The nature and the magnitude of the antiferromagnetic exchange have been discussed on the basis of the structural features.
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  • 91
    ISSN: 1434-1948
    Keywords: Alkenylcarbynes ; Dinuclear tungsten complexes ; Electrochemistry ; Tungsten NMR ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Neutral trans-cyanide alkenylcarbyne complexes 2a and 2b have been prepared by reaction of the complex 1a and 1b with NaCN or [Bu4N]CN. The reaction of complexes 2a and 2b with an equimolar amount of the acetonitrile complexes 1a and 1b in CH2Cl2 leads to the cationic cyanide-bridged bis(alkenylcarbyne) di-tungsten complexes 3a-d. Diisocyanide-bridged bis(alkenylcarbyne) di-tungsten complexes 4a and 4b have been synthesized by the reaction of complexes 1a and 1b with 0.5 equivalents of the diisocyanide 1,4-(CN)2C6H4. IR as well as 1H-, 31P{1H}-, 13C{1H}-, and 183W-NMR data are reported. The spectroscopic data show that in the dinuclear complexes 3a-d, the bridging CN group and the alkenylcarbyne units are located in trans positions, while in the dinuclear complexes 4a and b, the isocyanide groups of the bridging ligand 1,4-(CN)2C6H4 and the two alkenylcarbyne moieties are cis. The 183W chemical shifts of complexes 2a, 2b, 3a-d, 4a, and 4b were obtained through two-dimensional indirect 31P, 183W NMR recording techniques. A downfield shifting of 183W resonances of the cyanide-bridged dinuclear complexes 3a-d with respect to the mononuclear ones, 2a and 2b, was observed. The δ183W of isocyanide bridging dinuclear complexes 4a and 4b appear at higher field than those of the corresponding mononuclear cyanide 2a and 2b in accordance with the higher π-acceptor electron properties of the isocyanide ligand. The electrochemical behaviour of all the complexes has been investigated by cyclic voltammetry and controlled potential electrolysis in aprotic media and at a Pt (or vitreous C) electrode. Complexes 1, 2, or 3 undergo multi-electron irreversible oxidation processes involving anodically induced proton dissociation from the alkenylcarbyne ligands, and irreversible cathodic processes are also observed for all the complexes. The order of the redox potentials reflects that of the net electron π-acceptor/σ-donor character of the ligands and the ligating alkenylcarbynes are shown to behave as remarkably strong π-electron acceptors (even stronger than CO).
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  • 92
    ISSN: 1434-1948
    Keywords: Colloids ; Sol-gel processes ; Immobilization ; Heterogeneous catalysts ; Hydrogenations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A bimetallic, fully alloyed Pd/Au colloid of 3.0 nm particle size, obtained by the co-reduction of Pd and Au salts with tetraalkylammonium triethylhydroborate, was embedded in a silica matrix employing a modified sol-gel procedure with THF as the solvent. The removal of the protecting tenside led to a mesoporous texture with a comparatively narrow pore distribution. The physical characterisation by a combination of several techniques has shown that the SiO2-embedded Pd/Au colloid preserves the size and the structural characteristics of the colloidal metal precursor. The new material exhibits catalytic properties in selective hydrogenation.
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  • 93
    ISSN: 1434-1948
    Keywords: Thiacalixarene ; Trimetallic sandwich ; Cobalt ; Zinc ; Divergent receptors ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction between deprotonated p-tert-butyltetrathiacalix[4]arene and CoII or ZnII under strictly defined conditions leads to the formation of sandwich species in which a trimetallic unit is held between two opposed, divergently oriented, staggered O- and S-bound calixarene ligands in the cone conformation. Despite the isomorphous nature of the crystalline compounds, there is a subtle difference in the coordination of CoII and ZnII, presumably related to the differences in metal radius and electron configuration combined with structural restrictions imposed by the calixarene framework, in that whereas all three Co atoms may be considered six-coordinate (and approximately octahedral), only two of the Zn atoms appear so, the third being five-coordinate and more nearly trigonal bipyramidal in its coordination geometry.
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  • 94
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 831-834 
    ISSN: 1434-1948
    Keywords: Metallo-calixarenes ; Gold complexes ; Tetraphosphane ; Stability constants ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Assemblage of the tetragold complex [L·(AuCl)4] from p-tert-butyl-calix[4]-(OCH2PPh2)4 (L) and [AuCl(tetrahydrothiophene)] was investigated by NMR and UV/Visible spectroscopic titrations. Three steps could be resolved and are assigned, respectively, to addition of one, two and four AuCl units to the macrocyclic ligand. At each stage of metallation, symmetrical species persist on the NMR time scale since the bound AuCl fragments migrate between the different phosphorus centers via both intra- and intermolecular processes. The derived stability constants (logβ1 = 4.4 ± 0.2, logβ2 = 7.0 ± 0.7, and logβ4 = 14.5 ± 2.0) indicate both positive and negative cooperativity during build-up of the tetranuclear species. An X-ray diffraction study made with crystals obtained from an L:Au (1:2) mixture revealed the formation of an unusual binuclear complex whose solid state structure comprises a polymeric chain of [L·AuCl] units linked by pseudo-tetrahedral Au+ ions, each generic unit containing a pendant linear PAuCl fragment. This polymeric species, with its two distinct binding modes, provides a simple rationale by which to explain the role of cooperativity in the overall assembly process.
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  • 95
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 839-842 
    ISSN: 1434-1948
    Keywords: Tris(pyrazolyl)borate ; Tantalum ; Agostic interactions ; Alkyne complexes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of unprecedented alkyne hydrotris(3,5-dimethylpyrazolyl)borato (TpMe2) tantalum(III) complexes is reported. The parent dichloro complex TpMe2TaCl2(PhC≡ CCH3) (2) is obtained from TaCl3(DME)(PhC≡CCH3) and KTpMe2. 2 reacts with methyllithium to give the dimethyl complex TpMe2Ta(CH3)2(PhC≡CCH3) (3) and with ethylmagnesium chloride to give the X-ray characterized α-agostic ethyl complex TpMe2Ta(Cl)(μ-H-CHCH3)(PhC≡CCH3) (4). Reaction of 4 with methyllithium generates the mixed methyl ethyl complex TpMe2Ta(CH3)(μ-H-CHCH3)(PhC≡CCH3) (5) in solution. Spectroscopic data indicate that 5 is α-agostic at the ethyl group only.
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  • 96
    ISSN: 1434-1948
    Keywords: Sulfur ; Titanium ; Zinc ; Polysulfido complexes ; Sulfur heterocycles ; Polysulfides ; Polysulfanes ; Sulfenyl chlorides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation of seven novel organic polysulfanes is reported. Bis(n-octyl)heptasulfane R2S7 1 is formed upon reaction of RSCl with [Cp2TiS5], while the corresponding nonasulfane R2S9 2 is obtained by reaction of RSSCl with [Cp2TiS5]. The bis(n-octyl)pentasulfane R2S5 3 is obtained from RSCl and [(Cp′2TiCl)2S3] by transfer of the S3 ligand at 20 °C. The new alkyl polysulfanes 1-3 have been obtained in quantitative yields. They are liquids at 20 °C, having freezing points below -50 °C, but do not form mesogenic phases. Reactions of [Cp2TiS5] with 2-naphthyl- and 4-chlorophenyl sulfenyl chloride furnish the corresponding heptasulfanes 4 and 5, respectively, which are solids at 20 °C. 1,2-Benzodisulfenyl chloride C6H4(SCl)2 reacts with [(Cp′2TiCl)2S3] to give the known 1,2,3,4,5-benzopentathiepin C6H4S5 6, with [Cp2TiS5] to give the novel 1,2,3,4,5,6,7-benzoheptathionin C6H4S7 7, and with [(TMEDA)ZnS6] to give the novel 1,2,3,4,5,6,7,8-benzooctathiecin C6H4S8 8. The cyclic polysulfanes 6-8 are solids at 20 °C and have been recovered in yields of 60-83%. The orthorhombic structure of 1,2-C6H4S7 has been investigated by single-crystal X-ray diffraction analysis. The molecules are found to be located at sites of Cs symmetry and the motif of the C2S7 heterocycle is +-+-+-+-, with the torsion angle of zero at the carbon-carbon bond. The three internuclear SS distances measure 205.0(1), 203.7(1), and 205.7(1) pm.
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  • 97
    ISSN: 1434-1948
    Keywords: Palladium ; Platinum ; Dithiolenes ; Diselenolenes ; Sulfur ; Selenium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tetrachalcogenides [ME4(dppe)] (M = Pd, E = S; M = Pt, E = S, Se) react with the activated alkynes RO2CC≡CCO2R (R = Me, Et) to form the dithiolenes and diselenolenes [M{E2C2(CO2R)2}(dppe)]; the structures of the compounds with E = S, R = Et have been determined by X-ray crystallography; [PdS4(dppe)] also reacts with the carbene complex [W(CO)5{C(OEt)C≡CPh}] to yield the bimetallic dithiolene [Pd{S2C2[C(OEt)W(CO)5]Ph}(dppe)].
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  • 98
    ISSN: 1434-1948
    Keywords: Pyrazolate complexes ; Palladium ; Platinum ; N ligands ; Bridging ligands ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Trinuclear complexes containing pyrazolate bridging ligands of the type [NBu4]2[{(C6F5)2 M(μ-pz)(μ-X)}2M′] (M, M′= Pd or Pt; X = Cl, OH, or pz) (Hpz = pyrazole) have been prepared using [NBu4][M(C6F5)2(acac)] (acac = acetylacetonate) or [NBu4]2[M2(C6F5)4(μ-OH)2] and [M′Cl2(Hpz)2] or [M′(Hpz)4]2+ as starting materials. Asymmetric homo- and heterobimetallic complexes of the types [NBu4][R2M(μ-pz)2Pd(η3-allyl)] and [R2M(μ-pz)2M′L2] (allyl = C3H5 or C4H7; L2 = 2 PEt3 or bipy; R = C6F5 or C6Cl5; M, M′ = Pd or Pt) have been obtained starting from [NBu4][MR2(pzHpz)] and [Pd(η3-allyl)(acac)] or [M′L2Cl2], respectively. The identity of the new complexes has been established by NMR (1H, 19F and 31P) spectroscopy. The crystal structure of [{(C6F5)2Pd(μ-pz)(μ-Cl)}2Pd]2- has an inversion centre, with a bent appearance of the Pd3(μ-pz)2(μ-Cl)2 moiety. The crystal structure of [(C6F5)2Pd(μ-pz)2Pd(η3-C4H7)] has also been determined by single-crystal X-ray diffraction, where a boat conformation of the central “Pd2N4” six-membered rings is observed.
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  • 99
    ISSN: 1434-1948
    Keywords: Copper ; Nickel ; Amides ; Polynuclear complexes ; Magnetic properties ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New homo- and heterometallic hexanuclear complexes of formula {[Cu(tmen)(H2O)]2[Cu(tmen)]2[Cu2L](H2O)}(ClO4)4 ·2 H2O [Cu6-tmen] {[Cu(pmdien)]4[Cu2L]}(ClO4)4 · 4 H2O [Cu6-pmdien] and {[Ni(cyclam)]4[Cu2L]}(ClO4)4 · 4 H2O [Cu2Ni4-cyclam] [H8L = tetrakis(aminomethylene)methanetetrakis(oxamic acid), tmen = N,N,N′,N′-tetramethylethylenediamine, pmdien = N,N,N′,N′,N″-pentamethyldiethylenetriamine, and cyclam = 1,4,8,11-tetraazacyclotetradecane] have been synthesized. The crystal structure of [Cu6-tmen] has been determined by single-crystal X-ray diffraction. The structure consists of cationic {[Cu(tmen)(H2O)]2[Cu(tmen)]2[Cu2L](H2O)}4+ hexanuclear units. The hexanuclear cation is made up of two symmetry-related oxamato-bridged trinuclear units connected through the central carbon atom C(6) of the L8- ligand. Variable-temperature magnetic susceptibility measurements (1.8-300 K) have been performed for these series of complexes including the dinuclear precursors of formula Na4[Cu2L] · 10.5 H2O [Cu2-Na], (NMe4)4[Cu2L] · 4 H2O [Cu2-NMe4] and (PPh4)4[Cu2L] · 6 H2O [Cu2-PPh4]. The magnetic data have been interpreted. Evidence of a weak intramolecular ferromagnetic interaction between the two CuII ions in [Cu2L]4- has been observed. For the hexanuclear species, the interaction through the oxamato bridge was found to be equal to -6790, -2650, and -1643 yJ (-342, -133, and -82 cm-1) for [Cu6-tmen], [Cu6-pmdien], and [Cu2Ni4-cyclam], respectively. In these complexes, the weak intramolecular ferromagnetic coupling between the two CuII ions within the dinuclear synthon was masked by intermolecular interactions or local anisotropy.
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  • 100
    ISSN: 1434-1948
    Keywords: Boron ; Transition metals ; Sandwich complexes ; Boratabenzene ; Pinene ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complexes of pinene-fused boratabenzene ligands [(1R,9R)6,10,10-trimethyl-4-boratatricyclo[7.1.1.02,7]undeca-2,4,6trienes] C13H17BX (with a: X = NMe2; b: X = OMe; c: X = Me) are described. The lithium salt Li(C13H17BNMe2) [Li(1a)] reacts with [Cp*Fe(NCMe)3]PF6 and with Mn(CO)3Br(py)2 to give diastereomeric mixtures FeCp*(C13H17BNMe2) (4a) and Mn(CO)3(C13H17BNMe2) (7). The mixture 4a undergoes solvolysis in methanol to produce methoxy compounds 4b, which in turn react with LiMe in Et2O to give methyl derivatives 4c. The lithium salts Li(C13H17BX) [Li(1a-c)] react with ZrCl4 in toluene or Et2O to give exo,exo-ZrCl2(C13H17BX)2 complexes (8a-c). The dimethyl derivative exo,exo-ZrMe2(C13H17BNMe2)2 (9) can also be prepared from 8a/LiMe in Et2O. NOE difference spectra have been analyzed to determine the configurations of the diastereomers and to establish a chemical shift criterion for assessing the configuration of the metal-ligand coordination. An independent confirmation of the product stereochemistries has been obtained by single-crystal X-ray structure determinations of exo-4a and 8a.
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