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  • 1
    Publikationsdatum: 2021-05-19
    Beschreibung: This document, which is directed at the fishing sector, researchers, conservationists and fishery administrators, was developed by researchers who are members of the Specialists Group for Marine Turtle Research and conservation in the Southwestern Atlantic Ocean (SWA) in response to the urgent need to evaluate the impact generated on sea turtles by fisheries. Historically, sea turtle conservation efforts have focused almost exclusively on the protection of nesting beaches. Nevertheless, over the last decade, research has proved incidental mortality as a result of fishing activities to be one of the greatest threats to these animals. This type of interaction is not only problematic for turtles, but also generates financial losses for fishermen and businesses. In spite of the efforts that are currently underway, researchers still do not have a detailed understanding of the impact that bycatch produces on sea turtle populations in the SWA. We have a long way to go before its effects can be minimized. Further research is needed regarding the biology and ecology of the various turtle species as well as the effective application of mitigation measures. The life cycles of sea turtles are long and complex. Turtles occupy various ecosystems (nesting beaches, coastal, neritic and oceanic zones, as well as pelagic and demersal areas) throughout their lifetimes, transcending various Exclusive Economic Zones and International Waters. The five species that inhabit the SWA region perform vast feeding and reproductive migrations, traveling through areas where many different fishing fleets operate. Therefore, sea turtles in the SWA interact with virtually all fisheries. These circumstances make it necessary to carry out biological, fishing related and conservation studies on a regional level. The efficiency of the existing international and national legal instruments has yet to be determined, in terms of their effectiveness in protecting sea turtles. In some cases, legislation that is specifically related to the interaction between fisheries and turtles does exist, such as those laws requiring the mandatory use of turtle excluding devices (TEDs). There are also explicit bans on sea turtle capture. Nevertheless, none of these regulations prevent sea turtle bycatch. Although some regional legal instruments are needed, these and the existing legislation will only be effective if they are accompanied by a broader range of permanent education and control measures, to achieve the commitment of all the parties involved. The ecosystem approach is gaining popularity among fishery administration organizations. Research and conservation efforts should also be moving in that direction. A regional and international effort is required in order to compile information regarding the bycatch produced by the various types of fisheries and fleets operating in the area. The enormous increase in fishing pressure that these fleets are exerting in this area has not been accompanied by an increase in information regarding the bycatch of species that have no commercial value. Pelagic longlining is one of the fishing methods, which must be most closely monitored, due to the high levels of bycatch that it produces, as well its ample distribution throughout the region, and the high level of fishing effort that it accounts for. Coastal trawlers and gillnetters must also be considered critical players, because they too produce a large rate of bycatch. These are the three types of fisheries that are most broadly distributed throughout the region, accounting for the majority of the fishing effort. Most of the institutions that work toward sea turtle conservation in the area have only begun to address the issue of bycatch over the last decade. This timeframe is reflected in the scope and quantity of the available publications, as well as the progress of activities directed at mitigating this problem. All of the institutions that have been mentioned in this report have made the gathering of information regarding interaction between sea turtles and fisheries one of their top priorities. Some institutions are even developing working programs for monitoring fisheries and testing mitigation measures. Many of these institutions have managed to develop adequate relationships with fishermen, ship owners and administrators. Nevertheless, limited access to funding is an obstacle to the development and testing of mitigation measures. The SWA network, which is a very valuable instrument that was created in 2003, has allowed the region’s institutions and researchers to exchange information and share their experience, in addition to lending each other support in carrying out joint activities, thus strengthening sea turtle conservation efforts. The capacity demonstrated so far by the region’s researchers and institutions, testifies to their ability to continue to make progress in knowledge generation and tests of bycatch mitigation measures.
    Beschreibung: Published
    Schlagwort(e): Fisheries ; Ecology ; Fishing gear ; Fisheries ; Ecology ; Fishing gear
    Repository-Name: AquaDocs
    Materialart: Book
    Format: 71 pp
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    facet.materialart.
    Unbekannt
    MGAP | DINARA
    Publikationsdatum: 2021-01-30
    Beschreibung: A partir de la firma del Proyecto de Gestión Pesquera DINARA-FAO (UTF/URU/025/URU), en septiembre de 2007, se comenzó a conformar una Unidad de Economía Pesquera. Sus objetivos se focalizaron en fortalecer la capacidad de recolección y análisis estadístico de la información socio-económica del sector. En el 2008 esta Unidad compiló y realizó un análisis de la información comprendida entre los años 2002 y 2007, reanudando luego de varios años esta publicación histórica. La misma fue un éxito en todo sentido, especialmente para consulta de los diferentes actores del sector. La aceptación y receptividad que ha tenido dicha publicación nos motiva y obliga a continuar en esta línea, rumbo a la obtención de un producto de valor y utilidad, basado exclusivamente en información oficial nacional. Este año retomamos la serie anual poniendo nuevamente a disposición de todos información actualizada, completa y de calidad que estamos seguros será nuevamente de gran beneficio para el sector público como privado, así como de interés para el público en general.
    Beschreibung: Published
    Schlagwort(e): Fisheries ; Trade ; Fishery statistics ; Fisheries ; Trade
    Repository-Name: AquaDocs
    Materialart: Book
    Format: 48
    Standort Signatur Erwartet Verfügbarkeit
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  • 3
    Publikationsdatum: 2021-05-19
    Beschreibung: Este documento, dirigido al sector pesquero, investigadores, conservacionistas y administradores de las pesquerías, surge como respuesta de investigadores pertenecientes al Grupo de Especialistas en Investigación y Conservación de Tortugas Marinas en el Atlántico Sud Occidental (ASO) a la urgente necesidad de evaluar el impacto de las pesquerías sobre las tortugas marinas. Históricamente, los esfuerzos referidos a la conservación de las tortugas marinas se han dirigido casi exclusivamente a proteger las playas de anidación. Sin embargo en la última década se ha podido comprobar que una de las mayores amenazas es la mortalidad incidental causada por las pesquerías. Esta interacción no implica únicamente un problema para las tortugas, sino que también genera pérdidas económicas para los pescadores y las empresas.
    Beschreibung: This document, which is directed at the fishing sector, researchers, conservationists and fishery administrators, was developed by researchers who are members of the Specialists Group for Marine Turtle Research and Conservation in the Southwestern Atlantic Ocean (SWA) in response to the urgent need to evaluate the impact generated on sea turtles by fisheries. Historically, sea turtle conservation efforts have focused almost exclusively on the protection of nesting beaches. Nevertheless, over the last decade, research has proved incidental mortality as a result of fishing activities to be one of the greatest threats to these animals. This type of interaction is not only problematic for turtles, but also generates financial losses for fishermen and businesses.
    Beschreibung: Cont. fotografías
    Beschreibung: Published
    Beschreibung: Sea Turtle, keeping
    Schlagwort(e): Fisheries ; Ecology ; Fishing gear ; Fisheries ; Ecology ; Fishing gear
    Repository-Name: AquaDocs
    Materialart: Book
    Format: 71
    Standort Signatur Erwartet Verfügbarkeit
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  • 4
    Publikationsdatum: 2021-05-19
    Beschreibung: El presente trabajo llama la atención a las recientes epidemias de intoxicación histamínicas reportadas en los Estados Unidos, debido al consumo del dorado (Coryphaena hippurus) o Mahi-Mah, contaminado. Esto dió como resultado la prohición de las importaciones de esta especie, proveniente de varios países entre ellos el Ecuador, y siendo el dorado una especie de relativa importancia económica en este país, dicha prohibición ha preocupado al sector pesquero. Los estudios llevados a cabo muestran claramente la susceptibilidad de esta especie a desarrollar histamina. Esto se debe principalmente a la temperatura a la que está expuesta, pues la demora antes de enhielar el pescado es la etapa crítica. Los resultados muestran un aumento exponencial de los niveles de histamina, en ciertos casos después de tan solo 9 horas de almacenaje a temperaturas ambientales entre 25-30°C. Los niveles de histamina en pescado muestreado en el mercado local fueron tan altos como 250 mg/100g de muestra. Se demuestra que el problema se debe fundamentalmente al mal manejo de la captura por parte de la flota artesanal, y la subsecuente falta de infraestructura adecuada para conservarla, es decir, no se enfría el pescado. Sin embargo, el estudio muestra que una reducción de la temperatura del pescado de solo 15° menos, podría dar como resultado un producto de mayor calidad. En el presente trabajo se hacen recomendaciones para establecer un nivel máximo permitido para la exportación de 10 mg%, y se comparan dos métodos rápidos de análisis.
    Beschreibung: Published
    Schlagwort(e): Fisheries ; Histamines ; Quality control ; Fisheries
    Repository-Name: AquaDocs
    Materialart: Journal Contribution
    Standort Signatur Erwartet Verfügbarkeit
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  • 5
    Publikationsdatum: 2021-05-19
    Beschreibung: 153 experimental sets were made with stackable Antillean fish traps in depths of 5 to 30 m in the waters around the Galápagos Island (Ecuador), between Octobre and April 1983. 1,885 fish were caught of 18 species mainly of the families Pomadasyidae, Acanthuridae, Sparidae and Serranidae. The mean catch rate was 5,5 Kg per lift or 0,4 Kg.h-1, and the mean weight of the fish caught was 0,45 Kg. The optimum set duration was found to be between 2 and 18 hours (possibly indicating a high rate of escape). This study took place during the period of the ”El Niño”, when catches of fish in this area generally were low, and it is not known what effect this had. The catches were good compared with other shallow areas, but the fishes caught were mainly of medium quality. It is thought that significant increases in the quantity and quality of the catch could be obtained with commercial traps in deeper areas, but the efficient use of these would require new vessels and equipment, and the resulting increase in fishing effort could lead to overfishing of the most acceptable species of reef fish. Hence the development of fishery using fish traps is not recommended for Galápagos. A study of the biology of the fish caught was carried out. A bibliography of references on fish traps and their use was compiled and is included.
    Beschreibung: Published
    Schlagwort(e): Fisheries ; Trap fishing ; Fisheries ; Catch statistics ; Trap fishing
    Repository-Name: AquaDocs
    Materialart: Journal Contribution
    Standort Signatur Erwartet Verfügbarkeit
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  • 6
    facet.materialart.
    Unbekannt
    Publikationsdatum: 2021-01-30
    Beschreibung: Le domaine maritime sénégalais s’étend de 18°00 N, -20°00 W, -16°30 E, 12°15 S ; la presqu’île du Cap-Vert située entre 14°30 N et 15°00 N le divise en deux zones aux caractéristiques topographiques distinctes. Au nord, le plateau continental est peu étendu vers le large et orienté Nord-Nord/Est. Au sud de la presqu’île, le plateau s’élargit et le talus continental est orienté nord-sud. L’embouchure du fleuve Sénégal au Sénégal au Nord de la presqu’île du Cap-Vert et celles de la Gambie et de la Casamance au Sud constituent également un trait marquant de cette région. Les travaux réalisés au Sénégal en océanographie ont montré : - l’existence de deux saisons marines aux caractéristiques très différentes qui se succèdent : une saison chaude de juillet à octobre et une saison froide de décembre à mai. Ces deux saisons sont séparées par des périodes de transition. Pendant la saison froide, les alizés (vent de secteur nord-ouest à nord-est) s’établissent et engendrent à la côte une résurgence d’eau profonde (upwelling) vers la surface ; - la mise en évidence de systèmes de grands courants aux caractéristiques différentes : le courant des Canaries et le contre courant équatorial ; - la description de trois grandes houles au large du Sénégal : o la houle de Nord-Nord ouest qui a lieu toute l’année o la houle de Sud-Sud ouest apparaissant pendant l’hivernage o la houle d’ouest possible aux environs du mois de novembre. Le littoral sénégalais représente une zone d’intérêt stratégique à la fois sur le plan démographique, économique et environnemental. Les milieux naturels, dans un état de conservation relativement préservé, produisent des ressources vitales pour les 11 millions d’habitants peuplant le Sénégal. L’économie nationale sénégalaise est très dépendante de ces ressources côtières et marines qui constituent les principales recettes en devises, qu’il s’agisse de pêche ou de tourisme. L’analyse de la situation et des tendances montre que la zone côtière fait l’objet de pressions diversifiées et de plus en plus lourdes. Ces pressions se traduisent souvent par des conflits d’intérêts entre les différents secteurs et par des impacts qui génèrent une dégradation de l’environnement et des conditions de vie des populations. Cette évolution risque ainsi de compromettre les potentialités de développement offertes par les 700 Km de littoral sénégalais. La pression démographique se développe préférentiellement sur la zone côtière qui accueille déjà près de 60% des habitants, notamment dans les centres urbains et les capitale, toutes situées en bord de mer, et qui continuent à recevoir des populations en provenance de l’intérieur, réfugiés climatiques ou économiques, ou simplement jeunesse attirée par les « lumières de la ville ». Cet exode, à l’origine de dysfonctionnements des systèmes de production ruraux qui manquent peu à peu de main d’oeuvre, contribue à son tour à générer des perturbations au niveau des centres urbains où la misère se substitue parfois à la pauvreté.
    Beschreibung: Les besoins en matériaux de construction consécutifs à cette évolution démographique entraînent des prélèvements massifs de sable sur les plages qui ont à leur tour des conséquences négatives sur l’érosion et la protection du littoral. La fragilisation des cordons dunaires augmente ainsi les risques d’inondations des terres, la ville de Saint Louis étant particulièrement vulnérable à cet égard. Les besoins en développement ont conduit à la réalisation d’infrastructures le long du littoral. Ces constructions, qui tiennent trop rarement compte des contraintes environnementales, ont entraîné des répercussions structurelles sur l’équilibre de la zone côtière. Ainsi, les barrages anti-sel, tel le barrage de Diama sur le fleuve Sénégal, ont entraîné des répercussions sur le fonctionnement de certains écosystèmes côtiers. En condamnant les influences des apports d’eau douce ils appauvrissent les milieux situés en aval, stérilisant peu à peu des zones riches en ressources ainsi que les économies et les cultures qui en dépendent. Le ralentissement des courants et la baisse de salinité en amont du barrage favorisent l’apparition de certaines plantes envahissantes, telles que la bilharziose ou le paludisme. Les effectifs de poissons dépendant de milieux à salinité variable sont directement affectés, expliquant par exemple une chute de près de 70% des captures dans le bas delta du Sénégal. Les besoins du développement se traduisent également par l’amélioration ou la création d’axes routiers qui, dans la majorité des cas, longent la zone côtière. Ces ouvrages entraînent des impacts directs sur l’environnement, tels la destruction des mangroves là où les routes barrent l’écoulement des marées (exemple de la route Samba Dia – Djifère. Les systèmes de production traditionnels sont en règle générale peu préparés à faire face à des circuits de commercialisation organisés à une échelle régionale ou internationale, où à des technologies plus performantes, et éprouvent des difficultés à maintenir un contrôle sur leur terroir. Faute de pouvoir opérer une métamorphose rapide de leur système de production, le risque existe de voir peu à peu disparaître des savoir-faire d’une grande valeur dans la gestion même de ces territoires et de leurs ressources et , plus généralement, des cultures qui leur sont associées. Le développement industriel exerce des impacts potentiels ou réels de grande magnitude sur la zone côtière et marine. Les secteurs les plus significatifs à cet égard sont le tourisme et les hydrocarbures. Concernant le premier, les infrastructures, principalement orientées vers le tourisme balnéaire, sont en grande majorité installées à proximité directe de la zone côtière. L’absence quasi généralisée d’études d’impacts approfondies et indépendantes a conduit à de nombreux échecs. Ainsi, la plupart des projets ont été pensés et réalisés sans tenir suffisamment compte des contextes socio-économiques, culturels et environnementaux dans lesquels ils s’insèrent. Certaines réalisations ont été planifiées sur des secteurs soumis à une forte érosion littorale, compromettant de façon irrémédiable non seulement les investissements mais l’utilisation ultérieure du site, comme cela s’est produit sur les plages au sud immédiat du Cap Skirring. Les questions relatives à la disponibilité en eau douce qui se posent de façon cruciale dans le Saloum par exemple, à la gestion des déchets et des eaux usées ne sont que rarement prises en considération de façon structurelle et durable, conduisant à la dégradation de l’environnement ou à des conflits avec les communautés locales qui nuisent à la qualité même du tourisme. L’exploration et l’exploitation des ressources en hydrocarbures représentent aussi un secteur d’intérêt stratégique avec une généralisation des prospections. Si la découverte de gisement d’intérêt commercial représente une opportunité majeure pour l’économie nationale, elle soulève néanmoins un certain nombre de questions au regard de l’environnement. En effet les des puits. Parmi ces risques nous pouvons citer les impacts des études sismiques sur les organismes marins, notamment poissons et cétacés, le rejet de fluides toxiques et déblais de forage, le déversement des eaux de production et les pollutions aiguës dues à des accidents intervenant pendant le forage, le stockage ou le transport. Le Sénégal en ce moment, en est au stade de la prospection. Toutefois, pour ce qui concerne le transport d’hydrocarbures, plus de 90 000 0000 de tonnes d’hydrocarbures transitent par les côtes sénégalaises. Les modèles de dérive des nappes élaborés par la Compagnie pétrolière Woodside en relation avec le champ de Chinguetti, actuellement en cours de production au large de la Mauritanie, montrent des probabilités d’impact sur les côtes allant du golfe d’Arguin jusqu’à Dakar, en cas d’accident. La surexploitation des ressources halieutiques constitue également un problème au niveau de l’environnement marin et côtier. En effet, si une partie de la fluctuation des biomasses peut s’expliquer par les changements du régime des upwellings, la baisse des captures s’explique par un effort de pêche excessif, que ce soit dans le sous-secteur industriel ou artisanal. A cette surcapacité vient s’ajouter la présence de flottes illicites non déclarées et non réglementées. L’utilisation de certains engins ou pratiques de pêche contribue à aggraver la situation : la pêche crevettière est à l’origine de prises accidentelles qui représentent jusqu’à 85 % du total des captures, incluant des espèces protégées comme les tortues marines, et qui sont rejetés à la mer . Les chaluts de fonds, qui vont pêcher jusqu’à 800 m de profondeur, ainsi que les dragues à coquillages entraînant des dégâts structurels sur les écosystèmes De plus l’influence des marchés à l’exportation exerce des pressions sélectives sur certaines espèces, les espèces démersales de poissons, céphalopodes étant les plus recherchées sur le marché. Les changements climatiques ont également des impacts négatifs sur l’environnement marin et côtier. On sait que l’élévation du niveau marin aura des répercussions directes sur les installations humaines littorales ainsi que sur les écosystèmes insulaires et côtiers. Des zones de mangroves entières qui ne disposent pas des conditions écologiques pour s’adapter peuvent disparaître, entraînant des risques accrus d’érosion et d’inondation. Ces mêmes risques se multiplient avec la fréquence accrue des épisodes météorologiques exceptionnels tels que les ondes de tempêtes capables de drosser les pirogues à la côte ou de provoquer la rupture de cordons dunaires. On sait par ailleurs que le réchauffement de la température des mers influe négativement sur la productivité des océans et la dynamique des courants tels que le courant profond originaire de l’antarctique et qui exporte vers le Sénégal et les autres pays de la sousrégion des sels nutritifs présents dans les upwellings. On observe également une diminution de la puissance des alizés qui pourrait avoir des répercussions directes sur la force des upwellings et donc sur la productivité des pêcheries et du milieu marin en général. La stratégie de réponse proposée combine une protection des zones côtières importantes et un reboisement des dunes littorales dans les secteurs de la côte nord et de la Flèche de Sangomar particulièrement menacés. L’évaluation économique de cette stratégie montre qu’elle est coûteuse mais nettement en deçà de la valeur économique des terres qu’elle sera amenée à protéger. Des efforts complémentaires devront cependant être faits pour évaluer le coût d’autres solutions de protection telles que le nourissement artificiel des plages. Par ailleurs, la stratégie envisagée ne répondant qu’à l’un des impacts des changements climatiques, à savoir les inondations, toute une série de mesures dites d’accompagnement ont été suggérées qui visent à diminuer la vulnérabilité en gérant mieux les ressources présentes dans la zone côtière, en développant les techniques de récupération des sols salés et en prenant des mesures législatives et institutionnelles appropriées. Enfin, il est très important de souligner que ces différentes mesures ne devraient être envisagées que dans un cadre plus global de gestion intégrée des zones côtières, seul à même d’assurer la participation de l’ensemble des acteurs concernés, l’éducation, la recherche et l’information environnementales mais aussi la cohérences et le suivi des mesures.
    Beschreibung: Ministère de l'Environnement, de la Protection de la Nature, des Bassins de Rétention et des Lacs Artificiels, Dakar (Sénégal)
    Beschreibung: Published
    Beschreibung: écosystéme marin; technique de pêche; filet; érosion côtière; pollution; pêche; flore; environnement; migration; pêcheur; oiseau d'eau; tortue marine; lamantin; requin; mammifére marin; réglementation; mangrove; écosystème; estuaire; delta
    Schlagwort(e): Deltas ; Ecosystems ; Marine environment ; Aquatic birds ; Fishermen ; Fisheries ; Mangroves ; Coastal erosion ; Flora ; Fishing nets ; Deltas ; Ecosystems ; Mangroves ; Coastal erosion ; Marine environment ; Marine mammals ; Shark fisheries ; Turtle fisheries ; Aquatic birds ; Fishermen ; Migrations ; Flora ; Fisheries ; Marine pollution ; Fishing nets ; Climatic changes
    Repository-Name: AquaDocs
    Materialart: Report , Non-Refereed
    Format: 1456859 bytes
    Format: application/pdf
    Format: 71
    Standort Signatur Erwartet Verfügbarkeit
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  • 7
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    Unbekannt
    Western Indian Ocean Marine Science Association
    Publikationsdatum: 2021-05-19
    Beschreibung: This paper examines the arrival of a new group of fishermen on the Kenyan coast and what this has meant for the state of fishery resources. It reviews four subject areas: access and the number of fishermen; the fishermen’s identity; the choice of fishing gear; and the fishing grounds selected. Data were collected from a small number of fishing households in the villages of Uyombo and Takaungu in Kilifi District, using mainly qualitative research methods. Local households on the Kenyan coast face increasing pressure on land as well as on marine resources. The declining economic situation and greater pressure on land have made people turn to fishing as an income-generating activity. This group of fishermen is referred to as the ‘new’ generation of fishermen as they have been involved in fishing for only one or two generations (including the current one) in contrast to the ‘old’ generation from families who have been fishing or in fishingrelated activities for much longer. The old generation of fishermen and their households have also diversified their incomes, with many fishing households turning to farming, for example, with women and grown-up children involved in various activities. The new generation of fishermen, mainly of the Mijikenda population group, has often been blamed for the loss of traditional access regulations and for using harmful fishing gear. This paper discusses the new generation of fishermen and their identity as they perceive it and relates this to employment generation as a policy measure for marine conservation.
    Beschreibung: Published
    Beschreibung: Artisanal fisheries;household survey; income diversification; marine conservation,
    Schlagwort(e): Fisheries ; Fishery resources ; Fisheries ; Fishery resources
    Repository-Name: AquaDocs
    Materialart: Journal Contribution
    Standort Signatur Erwartet Verfügbarkeit
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  • 8
    Publikationsdatum: 2021-05-19
    Beschreibung: FAO, Rome (Italie);Ministère du Développement et de l'Hydraulique, Dakar (Sénégal)
    Beschreibung: Published
    Beschreibung: Plan de développement; fôret; pêche; milieu continental; aquaculture; pisciculture ; bilan ; facteur climatique; facteur hydrologique ; facteur socio économique; population rurale; ressources naturelles; poisson d'eau douce; ressources naturelles; gestion de l'environnement; technique de pêche; commercialisation ; consommation; projet de développement
    Schlagwort(e): Natural resources ; Fisheries ; Aquaculture ; Marketing ; Development projects ; Forests ; Climatic data ; Hydrology ; Inland water environment ; Aquatic environment ; Development potential ; Fisheries ; Aquaculture ; Marketing ; Development projects ; Fish consumption ; Hydrology ; Inland water environment ; Aquatic environment ; Forests ; Socioeconomic aspects ; Climatic data ; Natural resources ; Freshwater
    Repository-Name: AquaDocs
    Materialart: Book
    Format: 412144 bytes
    Format: application/pdf
    Format: 32
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  • 9
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    Unbekannt
    American Association for the Advancement of Science (AAAS)
    Publikationsdatum: 2009-08-22
    Beschreibung: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Rick, Torben C -- Erlandson, Jon M -- New York, N.Y. -- Science. 2009 Aug 21;325(5943):952-3. doi: 10.1126/science.1178539.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Archaeobiology Program, Department of Anthropology, National Museum of Natural History, Smithsonian Institution, Washington, DC 20013, USA. rickt@si.edu〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/19696338" target="_blank"〉PubMed〈/a〉
    Schlagwort(e): Animals ; *Anthropology ; Archaeology ; *Ecosystem ; *Environment ; Fisheries ; Fishes ; Humans ; Marine Biology ; Otters ; Population Dynamics ; Sea Urchins ; Shellfish
    Print ISSN: 0036-8075
    Digitale ISSN: 1095-9203
    Thema: Biologie , Chemie und Pharmazie , Informatik , Medizin , Allgemeine Naturwissenschaft , Physik
    Standort Signatur Erwartet Verfügbarkeit
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  • 10
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    Unbekannt
    American Association for the Advancement of Science (AAAS)
    Publikationsdatum: 2009-05-30
    Beschreibung: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Morell, Virginia -- New York, N.Y. -- Science. 2009 May 29;324(5931):1132. doi: 10.1126/science.324_1132.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/19478158" target="_blank"〉PubMed〈/a〉
    Schlagwort(e): Animals ; Fisheries ; *Humpback Whale ; Oceans and Seas ; Population Dynamics ; Ussr
    Print ISSN: 0036-8075
    Digitale ISSN: 1095-9203
    Thema: Biologie , Chemie und Pharmazie , Informatik , Medizin , Allgemeine Naturwissenschaft , Physik
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  • 11
    Publikationsdatum: 2009-09-12
    Beschreibung: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Walker, Brian -- Barrett, Scott -- Polasky, Stephen -- Galaz, Victor -- Folke, Carl -- Engstrom, Gustav -- Ackerman, Frank -- Arrow, Ken -- Carpenter, Stephen -- Chopra, Kanchan -- Daily, Gretchen -- Ehrlich, Paul -- Hughes, Terry -- Kautsky, Nils -- Levin, Simon -- Maler, Karl-Goran -- Shogren, Jason -- Vincent, Jeff -- Xepapadeas, Tasos -- de Zeeuw, Aart -- New York, N.Y. -- Science. 2009 Sep 11;325(5946):1345-6. doi: 10.1126/science.1175325.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉The Commonwealth Scientific and Industrial Research Organisation (CSIRO) Sustainable Ecosystems, Canberra, ACT 2601, Australia. brian.walker@csiro.au〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/19745137" target="_blank"〉PubMed〈/a〉
    Schlagwort(e): Animals ; Climatic Processes ; Communicable Diseases/drug therapy/epidemiology ; Drug Resistance ; Ecosystem ; *Environment ; Fisheries ; Health ; Humans ; *International Agencies ; *International Cooperation
    Print ISSN: 0036-8075
    Digitale ISSN: 1095-9203
    Thema: Biologie , Chemie und Pharmazie , Informatik , Medizin , Allgemeine Naturwissenschaft , Physik
    Standort Signatur Erwartet Verfügbarkeit
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  • 12
    facet.materialart.
    Unbekannt
    American Association for the Advancement of Science (AAAS)
    Publikationsdatum: 2009-05-09
    Beschreibung: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Greene, Charles H -- Monger, Bruce C -- McGarry, Louise P -- New York, N.Y. -- Science. 2009 May 8;324(5928):733-4. doi: 10.1126/science.1173951.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Ocean Resources and Ecosystems Program, Department of Earth and Atmospheric Sciences, Cornell University, Ithaca, NY 14853, USA. chg2@cornell.edu〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/19423808" target="_blank"〉PubMed〈/a〉
    Schlagwort(e): Animals ; Atlantic Ocean ; *Climate ; Cold Temperature ; *Ecosystem ; Female ; Fisheries ; Gadiformes/physiology ; Ovum/physiology ; Pandalidae/*physiology ; Phytoplankton/*physiology ; Population Dynamics ; Reproduction ; Salinity ; Seasons ; *Seawater/chemistry
    Print ISSN: 0036-8075
    Digitale ISSN: 1095-9203
    Thema: Biologie , Chemie und Pharmazie , Informatik , Medizin , Allgemeine Naturwissenschaft , Physik
    Standort Signatur Erwartet Verfügbarkeit
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  • 13
    Digitale Medien
    Digitale Medien
    Springer
    Environmental management 20 (1996), S. 523-539 
    ISSN: 1432-1009
    Schlagwort(e): Water control ; Floodplain ; Fisheries ; Bangladesh ; Chandpur
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Energietechnik
    Notizen: Abstract Bangladesh is a very flat delta built up by the Ganges—Brahmaputra—Meghna/Barak river systems. Because of its geographical location, floods cause huge destruction of lives and properties almost every year. Water control programs have been undertaken to enhance development through mitigating the threat of disasters. This structural approach to flood hazard has severely affected floodplain fisheries that supply the major share of protein to rural Bangladesh, as exemplified by the Chandpur Irrigation Project. Although the regulated environment of the Chandpur project has become favorable for closed-water cultured fish farming, the natural open-water fishery loss has been substantial. Results from research show that fish yields were better under preproject conditions. Under project conditions per capita fish consumption has dropped significantly, and the price of fish has risen beyond the means of the poor people, so that fish protein in the diet of poor people is gradually declining. Bangladesh is planning to expand water control facilities to the remaining flood-prone areas in the next 15–20 years. This will cause further loss of floodplain fisheries. If prices for closed-water fish remain beyond the buying power of the poor, alternative sources of cheap protein will be required.
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  • 14
    Digitale Medien
    Digitale Medien
    Springer
    Environmental biology of fishes 45 (1996), S. 219-235 
    ISSN: 1573-5133
    Schlagwort(e): Ecology ; Behaviour ; Evolution ; Cichlids ; Fisheries ; Conservation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Synopsis Ecological conditions in tropical lacustrine systems are considered by focusing on the evolution, maintenance, exploitation and vulnerability of fish communities in the African Great Lakes. The exceptionally high biodiversities in the littoral/sublittoral zones of the very ancient, deep, clear, permanently stratified rift lakes Tanganyika and Malawi, are contrasted with the simpler systems in their pelagic zones, also with biodiversity in the much younger, shallower Victoria, the world's largest tropical lake.
    Materialart: Digitale Medien
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  • 15
    ISSN: 0947-6539
    Schlagwort(e): azadienes ; azepines ; cycloadditions ; Fischer carbenes complexes ; reaction mechanisms ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 4-Amino-1-azadienes 1 react with α,β-unsaturated Fischer carbene complexes at -40°C to give stereoselectively a variety of substituted 3H-4,5-dihydroazepines 3; similarly, 1-hydroxy-1-azadienes (α,β-unsaturated oximes) 6 afforded the corresponding azepine derivatives 7. Chiral, nonracemic carbene complexes 11 gave azepines 12-13 (d.e. = 40-44%) upon reaction with oxime 6a; the major isomers were obtained in a diastereomerically and enantiomerically pure form (45-50% overall yield) after crystallization. An X-ray structure of 12a allowed assignment of the absolute stereochemistry. The acid hydrolysis of azepines synthesized provided racemic and enantiomerically pure 1,6-dicarbonyl compounds (±)-5, (±)-9, and (-)-14, as well as diol (-)-15. The mechanism of the reaction of 1 and 2 was investigated by multinuclear (1H, 13C, 15N, and 183W) NMR characterization of four intermediates (A, B, C, and D) at low temperature. The experimental sequence of events involves: i) 1,2-nucleophilic addition of the unsubstituted imine nitrogen of 1 to the metal carbene function (zwitterion A, -60°C), ii) cyclization to the seven-membered ring with 1,2-migration of the pentacarbonyl metal (zwitterion B, -40°C), iii) reductive elimination and coordination of the metal to the amine nitrogen (intermediate C, -40°C), and iv) thermal decomplexation and tautomerization (intermediate D and compound 3, above -20°C).
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 16
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. cpi 
    ISSN: 0947-6539
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 17
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996) 
    ISSN: 0947-6539
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 18
    ISSN: 0947-6539
    Schlagwort(e): homolytic cleavage ; organometallic compounds ; photochemistry ; rhenium complexes ; time-resolved spectroscopy ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: MLCT excitation of the complexes [Re(R)(CO)3(α-diimine)] (R = Me, Et, benzyl (Bz); α-diimine = iPr-PyCa, R′-DAB) results in the homolysis of the Re-R bond leading to the formation of radicals R. and [Re(CO)3(α-diimine)]. as primary photoproducts. The quantum yield of this photoprocess is dependent on the alkyl group used. For R = Me, the quantum yield is low (10-2) and depends on the temperature and excitation wave-length, whereas for R = Et and Bz the quantum yield is near unity and independent of T and λexc. The reaction is shown to proceed via a σ(Re-R)π* excited state that is rapidly (〈 20 ps) populated by a nonradiative transition from the optically excited MLCT state. Time-resolved IR and UV/Vis absorption spectra studied in the ns-μs and ps-μs time domains, respectively, show that the σπ* excited state is rather long-lived (τ ≈ 250 ns) in noncoordinating solvents; the dissociation of the Re-R bond from this state is strongly accelerated by polar or coordinating solvents (τσπ*〈 20 ps). The σπ* excited state is spectroscopically characterized by a (presumably σπ* → MLCT) transition at approximately 500 nm and by CO stretching frequencies closely resembling their ground-state values. The relative energies of the MLCT and reactive σπ* states, controlled by the nature of the alkyl lig-and, determine the photoreactivity of the complexes.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 19
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 259-264 
    ISSN: 0947-6539
    Schlagwort(e): dendrimers ; high-spin molecules ; photochemistry ; polycarbenes ; solid solutions ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A “starburst”-type nonadiazo compound was designed and synthesized by using the cyclotrimerization of 3,5-dibenzylphenyl ethynyl ketone as a key step. The diazo compound was photolyzed in methyltetrahydrofuran solid solution at cryogenic temperatures and analyzed by means of Faraday magnetometry and EPR spectroscopy. While the m-phenylene-connected nonacarbene was predicted to have a nonadecet (S = 9) ground state, the magnetic data of the photoproduct was more consistent with a pentadecet (S = 7) species. The result was interpreted in terms of the intramolecular cross-linking between the carbene centers by the determination of both the amount and the multiplicity of the spin. In the “starburst”-type polycarbenes with extended branching, the reactive carbene centers are able to approach one another and thus appear to readily recombine. This study highlights one of the limitations of the extension of the carbene network by way of flexible “starburst”-type structures.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 20
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 382-384 
    ISSN: 0947-6539
    Schlagwort(e): asymmetric synthesis ; chirality ; enolates ; hydrogen bonds ; structure elucidation ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reaction of acetophenone with tetrabutylammonium hydroxide affords the tetrabutylammonium enolate of phenyl (2-hydroxy-2-phenyl)propyl ketone. The crystal structure of this chiral enolate shows intramolecular hydrogen bonding between the hydroxyl group and the enolate oxygen atom. Furthermore, the α-methylene units of the ammonium counterion form hydrogen bonds to the basic enolate C and O atoms and to the O atom of the hydroxy group. This three-point bonding occurs selectively on the Re,Re side, a phenomenon which may be responsible for the direction of diastereo-selectivity in the epoxide-forming reaction of the enolate with N-bromosuccinimide.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 21
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 390-397 
    ISSN: 0947-6539
    Schlagwort(e): band structures ; hypervalent bonding ; semiempirical calculations ; tellurium compounds ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The bonding in the recently reported Cs3 Te22 phase, which contains both Te8 rings and remarkable Te6 sheets, is studied by approximate molecular orbital theory. Our focus is on the geometric and electronic features of the unique 2,3-connected Te net found as a substructure in this phase. The calculations show that both the linear and T-shaped Te geometries in the 2,3-connected Te net of Cs3 Te22 are determined by their particular electron count. Both types of tellurium atoms are hypervalent; we make connections to other well known hypervalent molecules, such as XeF2, I3-, and BrF3. Several possible variations and distortions of this net are discussed, all of which are found to be less stable. The discrete crown-shaped Te8 units that appear in the phase show normal covalent bonding and should occur in smaller molecular entities, too. According to our computations, Cs3 Te22 should be metallic. Two structurally related phases, CsTe7 and Cs2 Te15, are suggested.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 22
    ISSN: 0947-6539
    Schlagwort(e): carbon-carbon coupling ; carbonyl complexes ; hafnium complexes ; ketenylidene complexes ; zirconium complexes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The biscyclopentadienyldicarbonyl derivatives of zirconium(II) and hafnium(II) ([MCp2(CO)2]; M=Zr, Hf) promote the reductive coupling of coordinated carbon monoxide to give, in the presence of N,N-dialkylcarbamtes of the tetravalent metals [M(O2CNR2)4], the ketenylidene complexes [M3Cp2(μ2-CCO)-(μ3-O)(O2CNR2)6] (1 a: M=Zr, R=Et; 1 b: M=Zr, R=iPr; 2: M=Hf, R=iPr). The yields of the isolated zirconium complexes are as high as 60%, while that of the hafnium derivative is 40%. The X-ray crystal structure analysis of 1 b shows that it consists of trinuclear molecules, with the three zirconium atoms held together by the bidentate C2O ligand, by the tridentate bridging oxide and by the bidentate carbamato groups. Labelling experiments with [ZrCp2(13CO)2] show that the ketenylidene ligand originates from the coordinated CO groups. These ketenylidene complexes, which are rare examples of compounds containing a CCO but no CO ligand, are characterized by an intense IR band at about 2015 cm-1, associated with the bridging C2O ligand. The ketenylidene group of 1 b was readily removed and replaced by a bidentate μ-oxo ligand of the same hapticity by reaction with carbon dioxide or acetone or by thermal decomposition. The resulting product [Zr3Cp2(μ-O)(μ3-O)-(O2CNiPr2)6] (3) crystallizes in the same space group as 1 b and with similar cell constants and bond parameters.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 23
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 458-461 
    ISSN: 0947-6539
    Schlagwort(e): ab initio calculations ; barbaralanes ; borabarbaralanes ; Cope rearrangement ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reaction of MgCOT(thf)x with tBuBF2 or PhBCl2 affords the first 9-borabarbaralanes 2 (C8H8BR, a: R = tBu; b: R=Ph). With the aminoboron dihalides BCl2NiPr2 and BCl2N(SiMe3)tBu 9-borabicyclo[4.2.1]-nona-2,4,7-trienes 3 (a: R=NiPr2, b: R=N(SiMe3)tBu) and the trans-9-borabicyclo[4.3.0]nona-2,4,7-triene 4 are obtained. The bicyclic compounds 3a and 3 b are converted into 9-borabarbaralanes 2c and 2 d, respectively, by irradiation in solution as well as by heating. All 9-borabarbaralanes 2 are fluxional in solution. In the crystalline state, the B-phenyl derivative 2b displays a well-ordered van der Waals crystal structure. The theoretical prediction that the degenerate Cope rearrangement in barbaralanes will be retarded by π-acceptor groups in the 9 position has been verified. Quantum chemical calculations employing density functional theory support and help interpret the experimental findings. The isoelectronic 9-barbaralyl cations, in contrast, have such high Cope barriers that other rearrangement pathways are followed instead.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 24
    ISSN: 0947-6539
    Schlagwort(e): density-functional theory ; liquid water ; molecular dynamics simulations ; NMR chemical shifts ; solvent effects ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The solvent effect on the NMR chemical shielding in liquid water is calculated from a combination of molecular dynamics simulations and quantum chemical calculations for protons and 17O. The simulations are performed with three different potentials, ab initio as well as empirical ones, to study the influence of the force field. From the liquid configurations obtained in these simulations, molecules are randomly chosen together with neighbouring molecules to give clusters of water typical for the liquid at the selected temperature and density. Different cluster sizes are studied. The clusters are treated as supermolecules in quantum chemical calculations of chemical shifts by sum-over-states density functional perturbation theory with individual gauge for localised orbitals. The influence of the quantum chemical method is studied with an ab initio coupled Hartree-Fock gauge including atomic orbitals calculations with different basis sets for a selected cluster. An average over clusters yields the chemical shielding in the liquid at the selected temperature and density. The calculated values for the gas-liquid shift, which are in best agreement with experiment, are -3.2 ppm (exp. -4.26 ppm) for the proton and -37.6 ppm (exp. -36.1 ppm) for 17O, but the results depend strongly on the chosen interatomic potential.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 25
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1053-1059 
    ISSN: 0947-6539
    Schlagwort(e): chalcogenides ; periodic trends ; redox reactions ; soft chemistry ; transition metals ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The increase in energy of the sp anionic band on going from oxides to the less electronegative sulfides, selenides, or tellurides (with a similar trend in neighboring columns) facilitates anion-cation redox interactions involving the d levels of transition metal cations and the sp levels of anionic species. The interactions can induce phase transitions or gradual change within a given structural model. When a cation is reduced by electron transfer to its d levels from the sp band, holes appear at the top of the latter. Interesting soft chemistry can be carried out based on redox processes that neutralize the holes with electrons. This approach also allows particular structural types to be stabilized. Three structural domains can be recognized amongst the transition elements: 1) on the left-hand side of the periodic table layered structures are observed involving M4+ and (chalcogen)2- ions; 2) formation of sets of metal-metal bonds is then observed, the geometry of which depends on both the initial electron population and the electron transfer to the metal; 3) on the right-hand side the metals in their highest oxidation state are no longer active, and the holes at the top of the sp band are taken up by a catenation of the anions, which can lead to full polymerization of the anionic sublattice.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 26
    ISSN: 0947-6539
    Schlagwort(e): cyclic voltammetry ; dendrimers ; metallodendrimers ; terpyridine ; X-ray photoelectron spectroscopy ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A series of iron-containing metallodendrimers from the zeroth to the third generation was synthesized and characterized. The iron(II) ion of these metal complexes is encapsulated within a hydrophobic polyether dendritic envelope. X-ray photoelectron spectroscopy analysis revealed that the bonding environment of the iron atom was essentially ronment of the iron atom was essentially the same in dendrimers of different generations. However, cyclic voltammetry studies indicated that the reversibility of the metal redox process decreased in the higher-generation dendrimers. These observations were similar to those of a related electrochemical study conducted on the redox protein cytochrome C, in which the decrease in electron transfer reversibility was explained as a result of the increasing remoteness of the metal ion of the higher-generation dendrimers from the electrode surface.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 27
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1112-1114 
    ISSN: 0947-6539
    Schlagwort(e): coordination ; crystal structure ; halogen compounds ; magnesium compounds ; structure elucidation ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: MgBr2·OEt2 (1), which is commercially available and has been examined by different methods in the past, was obtained in crystalline form as a by-product of the reaction of amine-stabilised A1C1 solution with mesitylene magnesium bromide. The following unexpected structure was obtained by X-ray techniques: five-coordinate magnesium centres form trigonal bipyramids, which are connected by two common bromine atoms into chains. Structural details and especially the relationship with solid MgBr2, MgBr2·(OEt2)2 and MgI2·(OEt2)2 (2) are discussed in order to illuminate the unusual bonding in 1.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 28
    ISSN: 0947-6539
    Schlagwort(e): iron complexes ; magnetic susceptibility ; Mössbauer spectroscopy ; phasetransitions ; spin crossover ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The iron(II) complex [Fe(bpp)2]-(CF3SO3)2 H2O (bpp = 2,6-bis(pyrazolyl-3-yl)pyridine) shows a thermal spin transition associated with a hysteresis of approximately 140 K width. The transition temperatures T1/2 (where the fraction of HS species γHS = 0.5) are 147 K and ≍285 K in the cooling and heating directions, respectively. The compound shows the LIESST and reverse-LIESST effects at low temperatures. The relaxation of the metastable HS states generated by LIESST was observed quantitatively at temperatures between 77.5 and 85 K by Mössbauer spectroscopy. Metastable HS states can also be generated by rapid cooling of the sample. The relaxation of the metastable HS states formed by thermal spin-state trapping was monitored at temperatures between 104 and 118 K by magnetic susceptibility measurements. The relaxation mechanisms of the HS states generated by LIESST and thermal spinstate trapping are completely different. We suggest that the HS → LS relaxation after thermal spin-state trapping is triggered by an additional structural phase transition of the system.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 29
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1164-1172 
    ISSN: 0947-6539
    Schlagwort(e): allylations ; allylsilanes ; double stereodifferentiation ; ephedrine ; homoallylic alcohols ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Enantiopure homoallylic alcohols 5, which are important building blocks in organic synthesis, are obtained with an ee of greater than 99% and a yield of 75-95% by cleavage of the secondary homoallylic ethers 4 using sodium in liquid ammonia. The ethers 4 are formed with excellent diastereoselectivity and in 52-89% yield by treatment of the aldehydes 1 with the trimethylsilyl ether of N-trifluoroacetylnorpseudoephedrine (2) in the presence of a catalytic amount of TMS triflate or TMS borontriflate, followed by addition of allylsilane 3. Nearly all achiral aliphatic aldehydes employed gave a diastereoselectivity of over 99:1. With the chiral aldehydes 24, the difference between matched and mismatched pairs was low; this reveals that there is strong reagent control.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 30
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996) 
    ISSN: 0947-6539
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 31
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1201-1203 
    ISSN: 0947-6539
    Schlagwort(e): alkali metals ; hydrogen ; metallic hydrogen ; metallization densities ; periodicity ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We examine the density-dependent metal-nonmetal transition (MNMT) for the Group 1 elements hydrogen, rubidium and caesium. Remarkably, the experimentally observed metallization densities agree closely with those predicted from the 1927 classical theory of K. F. Herzfeld, which outlines the critical conditions necessary for the metallization of any element of the periodic system. The metallization densities of the alkali metal elements are also consistent with the quantum mechanical theory of the MNMT, as first set out by Sir Nevill Mott.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 32
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996) 
    ISSN: 0947-6539
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 33
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1514-1517 
    ISSN: 0947-6539
    Schlagwort(e): calcium compounds ; calorimetry ; nitrides ; ternary metal nitrides ; zinc compounds ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The energetics of ternary oxide formation is reasonably well understood, but little is known of the energetics of ternary nitride formation. We have developed new procedures for high-temperature oxide melt solution calorimetry on metal nitrides and employed them to study compounds in the Ca/Zn/N system. The calorimetry utilized the easy reduction of MoO3 in the solvent to supply a pathway for rapid oxidation of “N3-” to N2 gas. These experiments represent the first high-temperature solution calorimetry of ternary metal nitrides. The results indicate that Ca3N2 acts as a basic nitride analogous to CaO in oxide systems, while Zn3N2 acts as an acidic nitride (“N3-” acceptor) in this ternary nitride system.
    Zusätzliches Material: 2 Tab.
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  • 34
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1509-1513 
    ISSN: 0947-6539
    Schlagwort(e): ab initio calculations ; binding studies ; crystal packing ; drug design ; hydrogen bonds ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In the design of novel protein ligands one of the major challenges is the replacement of functional groups to modify and improve the binding characteristics. Often nitrogen- and oxygen-containing groups are exchanged, or both atoms occur in a competitive situation. We have investigated the hydrogen-bonding abilities of oxygen atoms covalently bound to two non-hydrogen atoms of which at least one is formally assigned to an sp2-type hybridization. In particular, examples in which such oxygen atoms compete with nitrogen atoms in the same molecular segment have been studied. Based on interaction energies obtained from ab initio calculations for complexes of these molecules with water, the oxygen atoms can be classified as rather weak hydrogen-bond acceptors; nitrogen atoms present in the same fragment exhibit much stronger interaction energies. The ab initio results are confirmed by the relative frequencies with which oxygen and nitrogen atoms are found to be involved in hydrogen bonding in the crystal structures of organic molecules containing the fragments of interest.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 35
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1533-1536 
    ISSN: 0947-6539
    Schlagwort(e): catalysis ; dehydrogenations ; oxidations ; ruthenium complexes ; secondary alcohols ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Highly efficient ruthenium-catalyzed Oppenauer-type oxidations of secondary alcohols to ketones have been developed. The catalytic system consists of [(PPh3)3RuCl2] (1) and K2CO3 or [(C4Ph4COHOCC4Ph4)(μ-H)(CO)4Ru2] (2) in refluxing acetone. The catalytic reaction is of high efficiency and permits a catalyst: substrate ratio of 1:1000 at 56 °C. In some cases the initial turnover rate exceeds 1500 h-1. The reaction was found to be general and compatible with double bonds and oxidation-sensitive aromatics. With some allylic alcohols, isomerization to saturated ketones took place. The reaction proceeds by ruthenium-catalyzed dehydrogenation of the alcohol and subsequent hydrogen transfer to acetone. No primary kinetic isotope effect was observed for the catalytic reaction when α-deuterated 1-phenylethanol was employed as substrate (kH/kD=1.1); this shows that β-hydride elimination from a ruthenium alkoxide intermediate is not the rate-limiting step.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 36
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 4-6 
    ISSN: 0947-6539
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 37
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 7-8 
    ISSN: 0947-6539
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 38
    ISSN: 0947-6539
    Schlagwort(e): carbon ligands ; diynes ; iridium compounds ; metallacumulenes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reaction of [IrH2Cl(PiPr3)2] (2) with the pentadiyne derivative HC≡C—C≡C—CPh2OH (1) yields the five-coordinate compound [IrH(C≡C—C≡CPh2OH)Cl(PiPr3)2] (3), which photochemically rearranges to give the vinylidene-substituted isomer trans-[IrCl(=C=CH-C≡CPh2OH)(PiPr3)2] (4). On treatment of 3 with pyridine, the octahedral complex [IrH (C≡C—C≡CPh2OH)Cl(py)(PiPr3)2] (5) is formed. While attempts to eliminate water from 4 (or 5) failed, the reaction of 3 with one equivalent of trifluorosulfonic acid anhydride and two equivalents of triethylamine led to the formation of trans-[IrCl(=C=C=C=C=CPh2)(PiPr3)2] (6), which is the first neutral transition-metal complex containing a C5R2 ligand. The X-ray structural analysis of 6 reveals a perfect square-planar coordination geometry around the metal centre and an almost linear IrC5 chain with Ir-C—C and C—C—C bond angles of 174-179°.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 39
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 45-49 
    ISSN: 0947-6539
    Schlagwort(e): exchange processes ; kinetics ; NMR spectroscopy ; zirconium complexes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We have shown that it is possible to inhibit the transfer of magnetization in a system with several exchanging sites in dynamic equilibrium, as in a mixture of cis- and trans-ZrCl4L2 with excess free ligand L (L = (CH3O)3PO). The forward and backward reaction rates involving two selected sites can be studied while the effect of competing exchange processes is “quenched”. This can be achieved either by selective inversion of the magnetization of the two chosen sites in the course of the reaction interval, or alternatively by inversion of the magnetization of all other sites in the exchange network. The rate of exchange from the free to the cis site was determined to be kcis←free = 0.018 s-1. In the usual methods, this process would tend to be overshadowed by the almost two hundred times faster competing exchange process from the cis to the trans site (Ktrans←cis = 3.32 s-1).
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 40
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. cpi 
    ISSN: 0947-6539
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 41
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 9-18 
    ISSN: 0947-6539
    Schlagwort(e): ab initio calculations ; azaenolates ; NMR chemical shifts ; peptides ; Ramachandran maps ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Structures and conformations of the azaenolate lithium salts of amides (formamide, acetamide, and N-methylacetamide) and of the dipeptide model N-formylalaninamide were investigated by means of ab initio MO theory. Four possible structures of the lithiated C-enolates of acetamide were also included in the study. All structures were calculated at the HF/6-31+G(d) and MP2(fc)/6-31 + G(d)/HF/6-31 + G(d) levels; the lithiated azaenolates of formamide were also investigated at higher theoretical levels (up to MP4(fc)/6-311 + G(d,p)/MP2(fc)/6-311 + G(d,p)). For the lithiated azaenolates of all amides investigated, the most stable structure contains a four-membered ring in which the lithium ion is complexed by the oxygen and nitrogen atoms; the substituents attached to the carbon and nitrogen atoms of the azaenolate are in a cis arrangement. The lithiated azaenolates of acetamide are predicted to be more stable than the corresponding C-enolates. To simulate solvation, calculations on complexes of the lithiated azaenolates of formamide with up to three molecules dimethyl ether were also performed, and all azaenolates of amides were also reoptimized by ab initio reaction-field calculations. Both solvation models reduce the preference for lithium-chelated cis structures. The Ramachandran maps of the dilithiated bis(azaenolate) of N-formylalaninamide (having cis or trans arrangements of the azaenolate substituents) were scanned by MNDO calculations for conformational accessible regions. Thirteen stable structures were subsequently optimized at the HF/6-31 + G(d) ab initio level. The global minimum resembles a peptide in C7 conformation, but other conformations, not known for peptides, are close in energy. The structures of dimers of the lithiated azaenolates of N-methylacetamide and of glycinaldehyde were also calculated. The NMR chemical shielding of carbon, nitrogen, and oxygen atoms in all structures were predicted ab initio by using the gauge-including atomic orbital (GIAO) method.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
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  • 42
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 50-57 
    ISSN: 0947-6539
    Schlagwort(e): alkenes ; catalysis ; dihydroxylations ; electrophilicity ; ruthenium compounds ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Oxidative ruthenium catalysis (0.07 molequiv RuCl3·(H2o)3, 1.5 molequiv NaIO4, EtOAc/CH3CH3CN/H2O 3:3:1), beyond the usual C—C bond cleavage to give dicarbonyls, has been shown to syn-dihydroxylate a wide range of alkenes (except for strained bicyclic alkenes, sterically hindered trisubstituted alkenes, and most tetrasubstituted alkenes) to give vicinal diols rapidly (within minutes) and efficiently. The minor products are the usual oxidative fission products, namely, ketones and aldehydes or carboxylic acids, and sometimes ketols. Longer reaction times lower the yields of most diols, probably owing to oxidative glycol cleavage. Reactions with substrates containing one or more electron-with-drawing groups in conjugation with or adjacent to the alkene moiety are generally slower but give better yields. The diastereoselectivity of the present “flash” dihydroxylation, anti to the existing α-stereogenic center, with cycloalkenes is excellent whereas that with acyclic alkenes is moderate to poor. Sodium metaperiodate is still the best co-oxidant for the catalytic reaction. Aqueous acetonitrile (approximately 86%) as an alternative solvent system was found to give better yields of 1,2-diols than the original solvent system in some cases.
    Zusätzliches Material: 2 Ill.
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  • 43
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 475-475 
    ISSN: 0947-6539
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 44
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 502-510 
    ISSN: 0947-6539
    Schlagwort(e): alkynes ; C-glycosides ; cobalt complexes ; cyclizations ; enzyme inhibitors ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Reaction of gluconolactone 2 with allylmagnesium bromide at low temperatures afforded ketopyranose 3, which could easily be converted into open-chain ketoses (R)-6 and (S)-6. Their reaction with lithioacetylide 9 afforded propargylic alcohol derivatives (R)-10 and (S)-10, which could not be cyclized directly to the desired C-ketosides. They were converted by standard procedures into (R)-14 and (S)-14 and then into dicobalthexacarbonyl complexes (R)-16 and (S)-16. A facile acid-catalyzed ring closure gave the desired C-ketosides (R)-18 α/β and (S)-18α/β, respectively, in different ratios. In order to demonstrate that removal of the protective groups and hydrogenation of the CC triple bond proceed smoothly, (R)-18 α was transformed into the deprotected target molecule (R)-1 α. For the assignment of the new chiral centers at C-2/2′ and at C-8, (S)-18α was transformed into azido derivative (S)-22α, which underwent intramolecular cycloaddition to afford the spiro derivative (S)-25α. Because of the conformational constraints in this molecule, unequivocal configurational assignment was possible with the help of NMR data.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 45
    ISSN: 0947-6539
    Schlagwort(e): carbonyl complexes ; chiral ligands ; iron complexes ; phosphorus ligands ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Secondary phosphines such as HPPh2 and to the cationic iron dienyl complex [η5-(1R)-ethylnopadienyl)Fe-(CO)3]+ (1) by nucleophilic addition. The phosphonium salt initially formed is readily deprotonated to yield an optically active tertiary phosphine [(n4-(1 R)-ethylnopadienePPh2)Fe(CO)3] (2b). A similar reaction also occurs with [C6H7Fe-(CO)3]+ (3) and [C7H9Fe(CO)3]+ (4) to give [(C6H7PPh2)Fe(CO)3] (5) and [(C7H9PPh2)Fe(CO)3] (6) in good yields. The mechanism of formation of these novel phosphines is discussed. Complex 2 b crystallizes in the space group P212121 (no. 19); 5 crystallizes in the space group P21/c (no. 14). Like other monodentate optically active phosphines, 2 b is capable of coordinating to transition metal complexes. It forms palladium complexes on reaction with [{μ-chloro(allyl)palladium}2] as well as with [{μ-chloro[(N,N-dimethylamino-kN-2-methyl)phenyl-kC]palladium}2] (11). The latter reaction product crystallizes in the space group P31 (no. 144).
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 46
    ISSN: 0947-6539
    Schlagwort(e): carbohydrates ; cyclodextrin analogues ; cyclooligomerizations ; glycosylations ; nanotubes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An efficient polycondensation-cyclization approach to the synthesis of cyclodextrin analogues is demonstrated by the preparation of cyclohexaoside 1 and cyclooctaoside 2. The key intermediate, disaccharide 3, bearing the cyanoethylidene group as a glycosyl donor function and the trityloxy group as a glycosyl acceptor function was prepared in 15 steps starting from L-rhamnose and D-mannose. The crucial cyclooligomerization of the disaccharide monomer 3 was carried out in the presence of TrClO4 as a promoter with the use of ultra-dry conditions at normal concentrations. This reaction led to formation of the cyclic oligosaccharides 28 and 29 (in 34 and 31% yield, respectively), which were deprotected to afford 1 and 2, respectively. The X-ray crystal structural analysis of the cyclooctaoside 2 reveals a cylindrical shape for the cyclic oligosaccharide with C4 symmetry. Individual molecules of 2 are arranged perfectly in stacks that form nanotubes in the solid state.
    Zusätzliches Material: 14 Ill.
    Materialart: Digitale Medien
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  • 47
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996) 
    ISSN: 0947-6539
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 48
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 624-633 
    ISSN: 0947-6539
    Schlagwort(e): catenanes ; macrocycles ; rotaxanes ; self-assembly ; tetrathiafulvalenes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A general stepwise approach is described for the preparation of tetrathiafulvalene (TTF)-based linear and monoand dimacrocyclic compounds incorporating one or two 1,4-dioxyphenylene, 9,10-dioxyanthrylene, or 1,5- or 2,6-dioxynaphthylene units from readily available starting materials. By utilizing the π-π stacking interactions of the TTF unit with the dipyridinium dication of 1,1′-[1,4-phenylenebis (methylene)] bis-4,4′-bipyridinium bis(hexafluorophosphate), a rotaxane and two [2]catenanes were synthesized starting from the linear and monomacrocyclic compounds, respectively. From the dioxyphenylene-based dimacrocycle, three [3]pseudocatenanes (trans, cis, and a mixture of cis/trans isomers) were obtained with the trans compound as the major product. From the dioxyanthrylene dimacrocycle, only the trans-[3]pseudocatenane was obtained. Catenane products were formed quantitatively from the 1,5-dioxynaphthylene dimacrocycle in a template-directed reaction, affording a trans-[3]pseudo-catenane together with a [4]pseudocatenane (mixture of cis/trans isomers). From the 2,6-dioxynaphthylene dimacrocycle, a cis-[3]pseudocatenane was obtained as the major product and a trans-[3]pseudocatenane as the minor one. For the [3]pseudocatenanes (i.e., both the cis and trans catenanes), in which the TTF units were clamped by the tetracationic macrocycle, isomerizations were completely prevented even in the presence of trifluoroacetic acid. All new rotaxanes and catenanes were characterized by electrospray mass spectrometry, and the cis- and trans- [3]pseudocatenanes were additionally investigated by 1H NMR spectroscopy. The electrochemical and spectral properties of the rotaxane and the catenanes are reported. Catenane formation increases the redox potentials of the TTF unit. The results demonstrate the versatility of TTF as a building block in the construction of supramolecular structures.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 49
    ISSN: 0947-6539
    Schlagwort(e): chemoselectivity ; cinchona alkaloids ; clathrates ; osmium tetroxide ; spiro compounds ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Hydrobromination of quinidine (1) with fuming HBr furnished diastereomeric secondary bromides 2a and 2b in 82% yield. After acetylation the resulting bromides 2a-Ac and 2b-Ac could be separated na dconverted stereospecifically into ethylidene rubanes Z)-4 and (E)-4, respectively. cis-Dihydroxylation of (Z)-olefin 4 with OsO4 was shown to be feasible by two catalytic variants, giving the two diastereomeric diols 5a and 5b, separable by chromatography. A simple onepot procedure was developed for converting the sterically hindered 1,2-secondary, tertiary diols stereospecifically into spiroepoxides (5a 6a-Ac; 5b 6b-Ac). Our procedure involves overall inversion of configuration. The procedure complements the Kolb-Sharpless route to epoxides from 1,2-disecondary diols with overall retention of configuration. The other two diastereomeric spiroepoxides 6c and 6d were prepared in one pot under different conditions (chloramine T, then alkali). Two unprecedented tricyclic allylic N,O-acetals (Z)-7 and (E)-7 were also obtained. The structure of spiroepoxide 6c (as a CH2Cl2 monosolvate) and of tricyclic olefinic N,O-acetal (E)-7 was corroborated by X-ray crystallography.
    Zusätzliches Material: 1 Ill.
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  • 50
    ISSN: 0947-6539
    Schlagwort(e): asymmetric alkylations ; chiral auxiliaries ; kinetics ; organolithium compounds ; stereoselective syntheses ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Complexation of the configurationally labile α-phenylselenoalkyllithium compound 8 with 1,2-bisdimethylaminocyclohexane 15 led to two diastereomeric complexes 13 and 14 in a 7:3 ratio. Owing to ligand acceleration the complexes 13 and 14 added more rapidly to benzaldehyde than the uncomplexed organolithium compound 8. Trapping of complexes 13 and 14 by benzaldehyde was shown to occur more rapidly than their equilibration. This corresponds to non-Curtin-Hammett kinetics, in which enantiomeric enrichment in the products reflects the equilibrium ratio of the complexes 13 and 14.
    Zusätzliches Material: 1 Ill.
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  • 51
    ISSN: 0947-6539
    Schlagwort(e): amphiphiles ; cytomimetic chemistry ; phosphitylation ; polyprenols ; vesicles ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Identical- and mixed-chain di(polyprenyl) phosphates, derived from 3-methyl-2-buten-1-ol, (E)-geraniol, (E,E)-farnesol, (E,E,E)-geranylgeraniol, (R)-citronellol, or (R)-tetrahydrogeraniol have been synthesized by phosphitylation and oxidation with iodine/water. These phosphates gave organized systems in water, in particular vesicles, the physical properties of which were studied by photon correlation spectroscopy, electron microscopy, entrapment of a fluorescent dye (calcein), 31P NMR, stopped-flow/light-scattering studies, and fluorescence polarization with lipophilic probes. Interdigitation of mixed-length phosphates was not found to have any favorable effect on the stability of the vesicles. The C〉15 vesicles were formed despite the fact that they are composed of only one molecular species and are devoid of any reinforcer, but those with two geranyl chains appeared to be rather fragile. Phosphates containing C5 chains are soluble in water. The results obtained lend weight to the hypothesis that polyprenyl phosphates might have been primitive membrane constituents, and stimulate the search for appropriate reinforcers.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 52
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 812-814 
    ISSN: 0947-6539
    Schlagwort(e): alkanes ; cracking ; isomerizations ; sulfur compounds ; superacids ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A novel family of inorganic aprotic superacids has been found. Oxochlorides and chloride of sulfur combined with aluminium halides (SOCl2·n AlX3, SO2Cl2·n AlX3, MeSO2Cl·n AlX3, CF3SO2Cl·n AlX3, S2Cl2·n AlX3; n = 2 or 3, X = Br or Cl) are found to be effective promoters for the cracking and isomerization of alkanes at room temperature.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 53
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 832-837 
    ISSN: 0947-6539
    Schlagwort(e): cyclophanes ; macrocyclisations ; molecular ribbons ; nanostructures ; repetitive syntheses ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The longest molecular ribbons known to date (3-10), composed of a series of [3.3]metacyclophane units, have been synthesised by means of a repetitive synthetic strategy. These multiple ring systems with up to nine bridged benzene rings in a row are the longest structurally perfect cyclophane sequences known to date. The synthetic strategy comprises three steps: ester reduction to a tetrakis(hydroxymethyl) compound, derivatisation to the corresponding tetrakis(bromomethyl) derivative, and double cyclisation with the new key building block 14, which was especially developed for this sequence. Single-crystal X-ray analyses (3 a-7 a) and 1H NMR spectroscopy (3-10) show that, regardless of their length, these molecules adopt zigzag folded all-syn conformations. π-Stacks of nanometre dimensions are thus formed.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 54
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 869-876 
    ISSN: 0947-6539
    Schlagwort(e): ab initio calculations ; silaguanidinium cations ; silylium cations ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Quantium mechanical calculations at the MP2/6-31 G(d) level are reported for the silaguanidinium cation Si(NH2)3+ (1) and derivatives thereof. The equilibrium structure 1a has D3 symmetry with planar amino groups rotated out of the SiN3 plane by 19.60. The Si-N bond length of 1 a (1.658 Å) is intermediate between a single and a double bond. Isodesmic reactions show that the stabilization of the silylium cation 1 a by the amino groups (63.5 kcal mol-1) is about 40% of the resonance stabilization of the guanidinium cation (159.3 kcal mol-1), but 1 a is clearly better stabilized than alkyl-substituted silylium cations. The electronic stabilization of 1 a by the amino groups is also made obvious by the calculated complexation energy with one molecule of water. The calculated stabilization through complexation of water at HF/6- 31 G(d) is markedly lower for Si(NH2)3-(H2O)+ (6) (28.8 kcal mol-1) than for SiMe3(H2O)+ (40.6 kcal mol-1). The tris(dimethylamino) silylium cation Si(N-Me2)3+ (8) is even more stable than 1 a. The complexation energy of Si(NMe2)3-(H2O)+ (10) is only 17.3 kcal mol-1. IGLO calculations of the 29Si N M R chemical shifts predict that 1 a and 8 should not show the same extremely low shielding that is calculated for alkyl-sub-stituted silylium ions. The calculated 29Si resonances for 8 are in reasonable agreement with the experimental N M R spectrum of (Me2N)3 SiB(C6F5)4. AM 1 calculations predict that the substituted tripyrrolidino silylium cation 12 would be an even better candidate for a stable tricoordinate silylium cation in condensed phases. One of the pyrrolidine rings of 12 has tert-butyl groups in the 2 and 5 positions, which serve as a steric fence around the silicon atom.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 55
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 894-900 
    ISSN: 0947-6539
    Schlagwort(e): aza-Claisen rearrangement ; azoniones ; indolizidinones ; ring contractions ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The zwitterionic aza-Claisen rearrangement of optically active 3-pyrrolidine acryl esters and various acid chlorides to generate optically active azoninones proceeds with high simple diastereoselectivity (internal asymmetric induction) and a complete 1,3-chirality transfer. The reaction path observed depends on the subsitution pattern of the allylic system: while the more electron-rich alkylated allyl amine fromed predominantly von Braun type products, the α,β-unsaturated esters could be rearranged with high yields. The azoniones thus obtained were treated with electrophiles, inducing regio- and diastereoselective transannular ring contractions. The resulting indolizidinones should be useful key intermediates in alkaloid synthesis.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 56
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1014-1023 
    ISSN: 0947-6539
    Schlagwort(e): alkoxy radicals ; cyclizations ; pyridinethiones ; radicals ; tetrahydrofurans ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A series of hitherto unknown N-(pent-4-enyl-1-oxy)pyridine-2(1 H)-thiones (6) were prepared from substituted pent-4-enyl tosylates or benzylic chlorides. On irradiation with incandescent light heterocycles 6 liberated alkoxy radicals 2, which were studied for rearrangement reactions. Surprisingly, all transformations involving the 1-phenylpent-4-enyl-1-oxy radical (2a), for example, to give the substituted thioether 8, 2-bro-momethyl-5-phenyltetrahydrofuran (11), or the tetrahydrofuran 14a, were not stereoselective. On the other hand 2-, 3- mono-, and 1,5-disubstituted pent-4-enyl-1-oxy radicals 2d-e and 2g cyclized in good yields and with good to excellent stereoselectivities to give the corresponding 2,4-cis- and 2,3-trans-phenyltetra-hydrofurfuryl radicals 3d-e, and the trans-2-benzyl-5-methyl substituted intermediate 3g. The major reaction mode of the 4-phenylpent-4-enyl-1-oxy radical (2f) was the 6-endo cyclization, which afforded 3-phenyltetrahydropyran (13f) as the major product (endo:exo = 93:7) after trapping with hydrogen donors. According to the experimental data of the present study, the unusual reactivity of the 1-phenylpent-4-enyl-1-oxy radical (2a) in 5-exo-trig ring closures could be caused by a coplanar arrangement of the benzyloxy moiety in the transition state of the cyclization. This interaction would lock the radical center in 2a in a preferred conformation, which would result in similar steric effects for both cis- and trans- cyclizations.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 57
    ISSN: 0947-6539
    Schlagwort(e): ab initio calculations ; iron oxide ; iron sulfide ; mass spectrometry ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The electron-transfer behavior of the binary iron chalcogenides FeO and FeS has been examined by means of mass spectrometry and ab initio calculations using the averaged coupled-pair functional (ACPF) method. The experimental and theoretical results are in good agreement with each other and also with previous studies. The ionization energies (IE) of the diatomic species are found to be IE(FeO) = 8.8±0.2 eV, IE(FeO+) = 17.9±0.4 eV, IE(FeS) = 8.3±0.3 eV, and IE(FeS+) = 16.3±0.5 eV. Two new diatomic dications, FeS2+ and FeO2+, are shown to exist as metastable minima on the corresponding potential-energy surfaces. The data enable an evaluation of the intrinsic gas-phase redox properties of FeS and FeO, and the comparison demonstrates that iron sulfide is more prone to undergo facile reduction and oxidation than iron oxide.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 58
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1251-1257 
    ISSN: 0947-6539
    Schlagwort(e): ab initio calculations ; benzenes ; electrophilic substitutions ; proton affinities ; QSAR ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An additivity rule for proton affinities (PAS) in polysubstituted benzenes is derived from the MP2(fc)/6-31 G**//HF/6-31 G* + ZPE(HF/6-31 G*) theoretical model by use of the concepts of homodesmic reactions and independent substituents. The performance of the additivity rule of thumb is very good; this is evidenced by the excellent agreement of the estimated PAS with the latest experimental data. We believe that the additivity should work for larger aromatic compounds too. The PA increments, which characterize the influence of each substituent on a particular site of the benzene ring undergoing electrophilic substitution, proved useful in discussing various chemical properties of this family of compounds.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 59
    ISSN: 0947-6539
    Schlagwort(e): borazine ; boron nitride ; materials science ; thin films ; titanium complexes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: For the first time, solid-gas reaction techniques have been used for the synthesis and processing of thin films of boron nitride. Clear to intensely colored blue BN films were grown on Si(100) substrates by the transformation of borazine (B3N3H6) with a titanium complex as initiator under flowing nitrogen gas. The thickness of the films ranged from 70 to 100 nm, as determined by Rutherford backscattering (RBS) and atomic force microscopy (AFM) analyses. The intensity of the blue color of the thin film can be correlated to its thickness. The composition of the film determined by RBS studies corresponds to the stoichiometric formula B0.49N0.45O0.06, and N/B and O/B ratios are found to be 0.92 and 0.12, respectively. Nitrogen contents determined by nuclear reaction analysis agree well with the RBS results. Moreover, Auger electron spectroscopy (AES) measurements show that no titanium is present in the films and confirm the composition determined by RBS studies. X-ray photoelectron spectroscopy (XPS) shows the presence of boron and nitrogen in the blue BN film. Electron spin resonance (ESR) experiments at 293 and 12 K indicate a single broad signal with a g value (g = 2.005) close to that of a free electron. This synthetic approach provides opportunities for the preparation of new thin-film materials and for the fundamental study of solid-gas reactions.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 60
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1292-1302 
    ISSN: 0947-6539
    Schlagwort(e): complexes with nitrogen ligands ; ruthenium complexes ; self-assembly ; supramolecular chemistry ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A series of mono- and dimetallic complexes of rack type containing a dinucleating bis-tridentate ligand and RuII-2,2′:6′,2′-terpyridyl (tpy) sites were synthesised and characterised. The 1H NMR spectra of the dimetallic complexes were correlated to structural features, and the crystal structures of the dimetallic complexes were determined. They provide information about the way in which the central substitutent affects the overall shape of the racks and the relative disposition of the metal centres, measured by the pinching angle of the bis-tridentate ligand and the convergence angle of the ancillary tpy units. The latter demonstrates that a CH3 group yields the least bent complex and indicates how parallel the tpy units are. The dimetallic racks exhibit metal-metal interactions mediated by the bis-tridentate ligands as indicated by electrochemical and spectroscopic methods. The bridging-ligand π* orbital and the dπ metal orbital are stabilised by complexation of a second metal. The results obtained provide guidelines for the design of extended racks bearing several metal centres in a linear arrangement, which also represent potential components of molecular electronic devices.
    Zusätzliches Material: 14 Ill.
    Materialart: Digitale Medien
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  • 61
    ISSN: 0947-6539
    Schlagwort(e): half-sandwich complexes ; peptide syntheses ; peptides ; rhodium complexes ; ruthenium complexes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Organometallic dipeptide ester complexes of the general formula [(L)M(Cl)(K2-NH2CH2CONCH2CO2R)] (1: L=Cp*, M=Rh, 2: L=Cp*, M=Ir, 3: L=η6-C6Me6, M=Ru) react smoothly with various α-L-amino acid esters in the presence of NEt3 to yield the tripeptide ester complexes [(L)M(Cl)(K2-NH2CHR'CONCH2CONHCH2CO2R)] (5-7). In the same fashion chloro K2-tetrapeptide ester complexes 10 and 11 are obtained either from tripeptide ester complexes or by subsequent addition of two equivalents of amino acid ester to a dipeptide ester complex. When the strong base NaOMe is used in the reaction of the diglycine ester compounds with amino acid esters. K3-tripeptide ester complexes 12 and 13 are produced, in which one of the two coordinated peptide nitrogen atoms is pyramidal. The hexamethylbenzene ruthenium complexes 13 with tripeptide ligands are formed with very high diastereoselectivity. A plausible reaction mechanism for the metal-promoted peptide synthesis is presented. Synthesis and isolation of the peptide esters proceeds without racemization.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 62
    ISSN: 0947-6539
    Schlagwort(e): additions ; fullerenes ; regioselectivity ; semiempirical calculations ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Three series of regioisomeric bisadducts of C60, namely, C62(anisyl)4 and the mixed systems C62(anisyl)2-(COOEt)2, and C61(COOEt)2(NCOOEt), were synthesized starting from the 1,2-monoadducts C61(COOEt)2 (1), C61-(anisyl)2 (2), and C60(NCOOEt) (4) by using the Bingel and Bamford-Stevens reactions, and nitrene additions. In the case of C61(COOEt)2(NCOOEt) the complete series of nine possible regioisomers were isolated for the first time. For steric reasons the cis-1 isomers of C62(anisyl)4 and C62(anisyl)2(COOEt)2 were not formed. The transannular [6,6] bonds in the cis-1 isomer 42 of C61(COOEt)2(NCOOEt) are closed. The properties and regioselectivities of formation of these bisadducts and their monoadduct precursors were compared with those of the series C62-(COOEt)4 and C60(NCOOEt)2, which we synthesized previously. In the additions to 1, 2, and 4 the preferred positions of attack are e and trans-3 for sterically demanding addends (e.g., combinations of C(anisyl)2 and C(COOEt)2) and cis-1, e, and trans-3 for sterically less demanding addends (e.g., combinations of N(COOEt) and C(COOEt)2). A detailed analysis of the MO structures, the experimental and calculated geometries of monoadduct precursors, and the stabilities of reaction products leads to the conclusion that the addend-independent cage distortion itself is responsible for the observed regioselectivities of bisadduct formations.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 63
    ISSN: 0947-6539
    Schlagwort(e): copper proteins ; cross-reactions ; electron-transfer reactions ; kinetics ; metalloproteins ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The electron self-exchange rate constant for the Type 1 blue copper protein umecyanin from horseradish roots has been determined as 6.1 × 103 M-1 S-1 at pH 7.5, I = 0.100 M, 25°C by an NMR line-broadening method. The value obtained is one of the lower self-exchange rate constants determined for this class of protein; this is attributed to the presence of positively charged residues near to the electron-transfer site. The self-exchange rate constants calculated by means of a Marcus analysis of data for the cross-reactions (25°C) of umecyanin with azurin and cytochrome c551 (both from Pseudomonas aeruginosa) are substantially less at 8.0M-1 S-1 and 13.9M-1S-1, respectively, and are independent of pH in the range 7.0-8.0, I = 0.100M. The discrepancy between the self-exchange rate constants obtained by these two different methods can be rationalised if it is assumed that umecyanin reacts with the two proteins employed in the cross-reaction studies through the same site, but that this site is different from that used for the self-exchange process. A comparison of the primary structure of umecyanin with those of other Type 1 copper proteins has revealed that a glutamine rather than a methionine is likely as the fourth ligand of Cu at the active site. Other comparisons are made with stellacyanin, and the electron-transfer reactivity of the two proteins is discussed.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 64
    ISSN: 0947-6539
    Schlagwort(e): kinetics ; metal-metal bonds ; molybdenum complexes ; multiple bonds ; tungsten complexes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The reaction between diarylthiones and [Mo2(OCH2tBu)6] in hydrocarbon solvents yielded [Mo2(OCH2tBu)6-(μ-S)(=CAr2)] by cleavage of the C=S double bond. The Lewis base adduct [Mo2 (OCH2tBu)6(μ-S) (=CPh2) (PMe3)] (2) has been crystallographically characterized; it contains six- and five-coordinate Mo atoms linked through μ-S and μ-OR groups. The rate of the cleavage of the C=S bond has been studied by variable-temperature 1H NMR in [D8]toluene. A Hammett plot shows that both electron-donating and electron-releasing substituents in the aryl groups enhance the rate relative to Ph2C=S. The activation parameters for cleavage of the C=S bonds in Ph2C=S, (p-MeOC6H4)2C=S, and (m-CF3C6H4)2C=S exhibit essentially identical values for ΔS
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 65
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1552-1555 
    ISSN: 0947-6539
    Schlagwort(e): block copolymers ; micelles ; mineralization ; nanostructures ; thin films ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Controlled mineralization of gold nanoparticles has been performed in a microemulsion of polystyrene-block-poly(2-vinylpyridine). The starting point was the formation of a thermodynamically stable dispersion of HAuCl4 in inverse micelles of the block copolymer in toluene, which became metastable when the gold was reduced. Kinetic control of the transformation allowed the following stages of the mineralization/coagulation process to be stabilized: 1) one gold particle per micelle, 2) aggregated micelles containing two or three gold particles, and 3) a state in which empty micelles coexist with larger polymer-stabilized gold particles. Distinctive variations in the spectra were observed depending on the particle size and whether two particles had formed a couple with orientation-dependent dipolar interactions.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 66
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1566-1571 
    ISSN: 0947-6539
    Schlagwort(e): amino acids ; asymmetric syntheses ; carbolines ; chiral auxiliaries ; Pictet-Spengler reaction ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Aromatic and aliphatic Schiff bases of tryptamine react with Fmoc- or phthaloyl-protected amino acid chlorides to form N-acyliminium intermediates, which, in the presence of titanium alkoxides at room temperature, undergo Pictet-Spengler reactions to give tetrahydro-β-carbolines with diastereomeric ratios of up to 99:1. The chiral auxiliary can be removed from the Pictet-Spengler adducts by means of a simple reduction. To rationalize the observed stereoselectivity a transition-state model is proposed in which the titanium atom coordinates both the carbonyl group of the N-acyliminium ion and the amino acid protecting group.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
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  • 67
    ISSN: 0947-6539
    Schlagwort(e): density functional calculations ; IR spectroscopy ; ruthenium complexes ; time-resolved spectroscopy ; UV ; vis spectroscopy ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The photophysical properties of the metal-metal bonded complexes [Ru-(E)(E′)(CO)2(iPr-DAB)] (E=Cl, E′=SnPh3, PbPh3; E=Me, E′=SnPh3, PbPh3; E=SnPh3, E′=SnMe3, SnPh3, GePh3; E=PbPh3, E′=PbMe3, PbPh3, GePh3; iPr-DAB=N,N'-diisopropyl-1,4-diaza-1,3-butadiene) have been studied. According to time-resolved emission, UV/vis and IR spectra, combined with density functional (DFT) MO calculations, the lowest excited state has triplet metal-to-ligand charge-transfer (3MLCT), triplet halide-to-ligand charge-transfer (3XLCT) or 3σ(E-Ru-E)π* character, depending on the nature and combination of the ligands E and E′. The 3σ(E-Ru-E′)π* state is a bound state whose lifetime is strongly influenced by the ligands E and E′. An exceptionally long lifetime (264 μs at 80 K) is observed for the 3σ(Sn-Ru-Sn)π* state of the symmetrically substituted [Ru(SnPh3)2(CO)2(iPr-DAB)] complex. The reason for this long lifetime is the fact that the excited state of this complex is hardly distorted with respect to the ground state, owing to the delocalised character of the σ(Sn-Ru-Sn) bonding orbital, which mixes strongly with the π* orbital of the iPr-DAB ligand. This delocalisation is also responsible for the unusually high oscillator strength of the σ → π* electronic transition in the visible spectral region.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 68
    ISSN: 0947-6539
    Schlagwort(e): antithrombotics ; enzyme inhibitors ; oligonucleotides ; oligosaccharides ; protecting groups ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Derivatization of the octadecathymidylate derivative 18 (T18 ODN) containing a free amine function with sulfo-SIAB® gave the corresponding iodoacetyl ODN 21. Conjugation of the latter with the thiol-containing pentasaccharide 17c gave pentasaccharide-ODN conjugate III, which exhibited anti-Xa and antithrombin activities of 173 U mg-1 and 5 U mg-1, respectively.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 69
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1585-1595 
    ISSN: 0947-6539
    Schlagwort(e): concave hydrocarbons ; cyclophanes ; host/guest chemistry ; ion-selective electrodes ; prismands ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Concave hydrocarbons, such as 1 (C36H36), 4 (C60H60), 5 (C54H48), and 6 (C60H52), represent three-dimensionally clamped analogues of π-prismands. They encapsulate small metal ions and accomplish metal-ion extraction from aqueous solution. Their remarkable selectivity allows applications such as incorporation in ion-selective electrodes. The synthetic route is based on well-established cyclophane methodology and, thus, offers a general approach to a whole family of concave hydrocarbons.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
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  • 70
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 139-148 
    ISSN: 0947-6539
    Schlagwort(e): asymmetric ; syntheses ; Diels-Alder reactions ; dihydropyrans ; Lewis acids ; oxabutadienes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The stereodivergent asymmetric hetero-Diels-Alder reaction of achiral and chiral 1-oxa-1,3-butadienes carrying an oxazolidine moiety with various enol ethers in the presence of different Lewis acids is described as a highly stereoselective and efficient approach to dihydropyrans, which can be used for the synthesis of carbohydrates. In the cycloaddition of the achiral oxabutadiene very good endo/exo selectivity was possible, and with the chiral oxabutadienes excellent 1,6-asymmetric induction was additionally observed. In the processes a reversal of facial selectivity occurs by changing the Lewis acid, allowing the synthesis of both enantiomers of the dihydropyrans with the same auxiliary. Thus, cycloaddition of 1 to 2 in the presence of Me2 AlCl gives predominantly the endo product 3 (3:4 = 10:1), whereas with SnCl4 the exo product 4 is obtained (3:4 = 1:15). The reaction of 7 and 1 a in the presence of Me2AlCl as promoter nearly exclusively yields the endo-I adduct 16 a (16 a+17 a:18 a+19 a = 〉 50:1; 16 a:17 a = 60:1), whereas with TMS-OTf the endo-II-product 17 a was obtained as the main component (16 a+17 a:18 a+19 a = 〉 50:1; 16 a:17 a = 1:7.9). The use of SnCl4 leads to a mixture of endo and exo, again, however, with excellent induced selectivity. A similarly good induction was obtained with the oxabutadiene 9 containing the new auxiliary 8. Also, other enol others 1 b-g were used, some of which afforded excellent induction. Mechanistic considerations are used to explain the results.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
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  • 71
    ISSN: 0947-6539
    Schlagwort(e): biomineralization ; medium-sized rings ; calcite ; crystal morphology ; glycoproteins ; polysaccharides ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The synthesis of 4,4,9,9-tetramethyl-1-oxa-cycloundecane-5,6,7,8-tetrone (9) and 5,5,10,10-tetramethyl-1-oxa-cyclotridecane-6,7,8,9-tetrone (10) has been achieved in a multistep procedure. The key steps in this synthesis were the ring closure of 23 and 24 to 25 and 26, respectively, and the oxidation of the triple bond with RuO2/NaIO4 to the dihydroxydiketones 31 and 32. Compound 9 is the first cyclic tetraketone for which an intramolecular donor-acceptor stabilization has been found. A strong transannular interaction between the ether oxygen and the C4O4 unit in 9 was detected by X-ray studies on single crystals of 9. The transannular distance is 2.7-2.8 Å. Further evidence for a strong transannular interaction was obtained from the comparison of the reduction potential and the first band in the UV/Vis spectrum with the corresponding values from other openchain tetraketones. These findings were substantiated by PE investigations on 9. The crystal structures of the dihydroxy-diketones 31 a and 32 a showed that, in the case of the eleven-membered ring (31 a), there are also short transannular distances between the ether oxygen and the C2O2 moiety (2.5 Å and 2.9 Å). In the case of the thirteen-membered ring (32 a), no transannular interactions were found in the solid state.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 72
    ISSN: 0947-6539
    Schlagwort(e): computer simulations ; high-pressure chemistry ; lanthanide complexes ; ligand exchange ; mechanistic studies ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We studied the microscopic mechanisms of the water exchange reaction between the hydration shells of lanthanide(III) ions (Ln = Nd, Sm, Yb) and bulk water by means of molecular dynamics simulations. In contrast to the residence time of a water molecule in the first hydration shell (τres (1st shell) = 1577, 170 and 410 ps for Nd3+, Sm3+ and Yb3+, respectively), that in the second hydration shell is nearly independent of the type of the cation and amounts to 12-18 ps. Along the lanthanide series a change in the coordination number from 9 to 8 is coupled to a changeover in the water exchange mechanism. The observed water exchange events on the [Nd(H2O)9]3+ aqua ion follow a dissociatively activated Id mechanism via an eightfold-coordinated transition state of square antiprismatic geometry. The lifetime of the transitory square antiprism varies between virtually 0 and 10 ps. The assignment of an Id mechanism (instead of a limiting D mechanism) is supported by the existence of a preferential arrangement between the exchanging water molecules (1800) and by the fact that the calculated average activation volume ΔV≠ = + 4.5 cm3 mol-1 is clearly smaller than the estimated activation volume ΔV≠lim ≈ΔV0 = + 7.2 cm3 mol-1 for a limiting D process. In the case of Sm3+ a ninth water molecule exchanges frequently between the first hydration shell and the bulk and maintains the coordination equilibrium between a [Sm(H2O)8]3+ and a [Sm(H2O)9]3+ aqua ion. The resulting trajectory pattern of incoming and leaving water molecules is an alternation of elimination and addition reactions and cannot be classified into the scheme of D, I or A mechanisms for substitution processes. The reaction volume ΔV0 for the coordination equilibrium [Sm(H2O)8]3+ + H2O → [Sm(H2O)9]3+ can be evaluated consistently both by a thermodynamic and a geometric approach. The observed exchange events for [Yb(H2O)8]3+ exhibit the characteristics of an Ia mechanism. The water exchange takes place via a transition-state geometry close to that of a tricapped trigonal prism and involves a slightly negative activation volume.
    Zusätzliches Material: 13 Ill.
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  • 73
    ISSN: 0947-6539
    Schlagwort(e): allylic alcohols ; gas-phase chemistry ; ions ; mechanistic studies ; nucleophilic substitutions ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A first demonstration of the existence of the concerted SN2′ mechanism in the gas phase was obtained by establishing the regioselectivity of the attack of a neutral nucleophile, such as MeOH, on several allylic oxonium ions. These were generated in the gas phase by the reaction of radiolytically formed GA+ acids (GA+=CnH+5 (n = 1, 2), iC3H+7, and (CH3)2F+) with trans- (1) and cis-2-buten-1-ol (2) as well as with 1-buten-3-ol (3). Firm evidence in favor of the concerted SN2′ pathway accompanying the classical SN2 one in these systems was obtained after careful evaluation of the extent of conceivable intramolecular isomerization both of the primary oxonium ions from GA+ attack on 1-3 before nucleophilic displacement by MeOH and of their substituted intermediates before neutralization. The intermediacy of free allylic ions in the nucleophilic substitution was ruled out by generating the ions by protonation of 1,3-butadiene and by investigating their behavior in exactly the same media employed in the substitution reactions. The regioselectivity of MeOH with the ionic substrates investigated showed the occurrence of nearly equally extensive SN2′ and SN2 pathways in the oxonium ions from 1 (SN2′ (57 ± 2%) and SN2 (43 ± 2%)) and 3 (SN2′ (54 ± 2%) and SN2 (46 ± 2%)), whereas, with 2, the SN2 (66 ± 2%) reaction prevailed over the SN2′ one (34 ± 2%). The role of intrinsic structural factors in determining the SN2′/SN2 branching in the selected oxonium ions is discussed.
    Zusätzliches Material: 3 Tab.
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  • 74
    ISSN: 0947-6539
    Schlagwort(e): cyclohexenols ; elimination reactions ; gas-phase chemistry ; mechanistic studies ; nucleophilic substitutions ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Our radiolytic study of the occurrence in the gas phase of concerted SN2′ reactions on several open-chain allylic oxonium ions generated in the gas phase from the attack of gaseous GA+ acids (GA+=CnH+5 (n = 1, 2), iC3H+7, and (CH3)2F+) on suitable substrates is now continued with cyclic allylic alcohols, such as 3-methyl-2-cyclohexen-1-ol (1) and 1-methyl-2-cyclohexen-1-ol (2), with both MeOH and NMe3 as neutral nucleophiles. With MeOH as the nucleophile, the substitution reaction exclusively takes place on 1 as the starting compounds, whereas when the substrate is 2 it is accompanied by extensive elimination. With NMe3, only the elimination reaction is observed in the same systems. The analysis of the isomeric distribution of the substitution and elimination products allows definition of the corresponding reaction patterns. As for open-chain oxonium ions, the nucleophilic attack on O-protonated 1 and 2 is preceded by significant intramolecular interconversion. Partial unimolecular dissociation of the same ionic intermediates also takes place. After careful evaluation of the extent of these side processes, it is demonstrated that the O-protonated 1 undergoes the concerted SN2 process with MeOH almost exclusively (≥ 99%). With O-protonated 2, how ever, the concerted SN2′ pathway (84-95%) prevails over the classical SN2 one (6-17%). Concomitant [1,2] (E2) and [1,4] elimination (E2′) pathways involve attack of the selected nucleophiles on the oxonium ions from 1 and 2. Their relative extent (E2′/E2:1.78-1.96 (1); 1.43-1 70 (2)) appears only slightly dependent on the nature of the ionic substrate, the nucleophile (whether MeOH or NMe3), and the leaving group (whether H2O or MeOH). The effects of both intrinsic structural factors and experimental conditions in determining the SN2′/SN2 and E2′/E2 branchings in the selected oxonium ions is discussed and compared with related gas-phase data.
    Zusätzliches Material: 9 Ill.
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  • 75
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 369-372 
    ISSN: 0947-6539
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 76
    ISSN: 0947-6539
    Schlagwort(e): crown ethers ; dialkylammonium salts ; hydrogen bonding ; molecular recognition ; pseudorotaxanes ; self-assembly ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A very simple self-assembling system, which produces inclusion complexes with pseudorotaxane geometries, is described. The self-assembly of eight pseudorotaxanes with a range of stoichiometries-1:1, 1:2, 2:1, and 2:2 (host:guest)-has been achieved. These pseudorotaxanes self-assemble from readily available components-well-known crown ethers, such as dibenzo[24]crown-8 and bis-p-phenylene[34]crown-10, and secondary dialkylammonium hexafluorophosphate salts, such as (PhCH2)2NH+2PF-6 and (nBu)2NH+2PF-6-and have been characterized not only in the solid state, but also in solution and in the “gas phase”. The pseudorotaxanes are stabilized largely by hydrogen-bonding interactions and, in some instances, by aryl-aryl interactions.
    Zusätzliches Material: 40 Ill.
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  • 77
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 737-741 
    ISSN: 0947-6539
    Schlagwort(e): Jahn-Teller distortions ; magnetic properties ; neutron powder diffraction ; nickel oxides ; X-ray powder diffraction ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The new phases MIIISr3NiIIIO6 have been prepared for M = Sc, In, Tm, Yb and Lu. Thermogravimetric analysis indicates that these phases are stoichiometric nickel(III) oxides. Rietveld refinement of their crystal structures from powder X-ray diffraction data confirms that they adopt the rhombohedral K4CdCl6- type structure (space group R\documentclass{article}\pagestyle{empty}\begin{document}$ \bar 3 $\end{document}c, a = 9.6595 (2) and c = 10.8546 (3) Å for ScSr3NiO6). The M site is fully occupied for M = Sc and In, but a deficiency of scattering for M = Tm, Yb and Lu is shown to be due to Ni substitution through a simultaneous refinement of the YbSr3NiO6 structure using X-ray and time-of-flight neutron diffraction data. The refined composition is (Yb0.83Ni0.17)-Sr3NiO6. The magnetic suseptibilities of the M = Sc, In and Lu samples show Curie-Weiss behaviour down to 6K; however, ScSr3NiO6 shows a broad transition between 250 and 290 K, with Curie-Weiss behaviour above and below this anomaly. This transition is thought to be between the statically and dynamically Jahn-Teller distorted regimes of octahedrally coordinated, low-spin Ni3+.
    Zusätzliches Material: 7 Ill.
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  • 78
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. cpi 
    ISSN: 0947-6539
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 79
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1330-1334 
    ISSN: 0947-6539
    Schlagwort(e): dendrimers ; exponential growth ; repetitive syntheses ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The synthesis of dendrons with orthogonally protected functional groups, which allows the construction of dendrons in an exponential fashion, is described. The sequence has been carried out on a gram scale for the first, second, and fourth generation. The dendrons have a relatively loose and flexible structure, which should make further growth feasible. Owing to the dendrons' adjustable and broadly applicable substitution pattern, they are the first representatives of a future construction kit for the systematic synthesis of layered dendrimers. The coupling step involves urethane formation.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 80
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1347-1351 
    ISSN: 0947-6539
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 81
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1359-1362 
    ISSN: 0947-6539
    Schlagwort(e): anhydrosugars ; enzymatic catalysis ; gangliosides ; glycoconjugates ; glycosidations ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A concise, regio- and stereoselective synthesis of the ganglioside GM3 has been achieved. Use of an α-1,2-oxirane derived from lactal facilitated installation of the anomeric β-ceramide side chain. Introduction of the sialic acid residue at C3, of the lactose was accomplished regiospecifically by enzymatically mediated sialyl transfer from CMP-Neu-5-Ac.
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  • 82
    ISSN: 0947-6539
    Schlagwort(e): clathrates ; cryptates ; helicates ; selfassembly ; zinc complexes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The structures of the hitherto unknown bis(double helicate) 10 and its cryptatoclathrate (10)2·2THF were unequivocally determined by X-ray diffraction. Bis(double helicate) 10 is formed in a one-pot synthesis starting from CH-acidic bis (tetrazolylmethyl ketone) 9 and Zn(OAc)2. The formation of racemic, homochiral 10 from [Zn2L32] fragments, which are formed in a self-assembly process, is governed by chiral self-recognition. According to NMR studies only 10 is present in solution. 13C CP/MAS NMR spectroscopy and X-ray analysis confirm aggregation of 10 with two molecules of THF to yield the inclusion compound (10)2·2 THF in the solid state.
    Zusätzliches Material: 6 Ill.
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  • 83
    ISSN: 0947-6539
    Schlagwort(e): ab initio calculations ; crystal structure ; halogen compounds ; nitrides ; selenium compounds ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Se2NBr3, a planar molecule shaped liked dividers, was formed by the reaction of SeBr4 with N(SiMe3)3, which reduced the selenium to the trivalent state. Under the same conditions, Se2NCl5 was obtained by the reaction of SeCl4 with N(SiMe3)3, retaining the tetravalent state of selenium. The molecule is formed by two edge-sharing pseudotrigonal bipyramids with selenium as their central atoms. Se2NCl5 reacts with PPh4Cl to form the Se2NCl-6 ion by the addition of a Cl- ion to only one of the two selenium atoms, resulting in pseudooctahedral coordination of this atom. Ab initio calculations for all the compounds reported confirm the experimentally determined structures.
    Zusätzliches Material: 7 Ill.
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  • 84
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1395-1398 
    ISSN: 0947-6539
    Schlagwort(e): bipyridine ligands ; helicates ; kinetics ; mass spectrometry ; self-assembly ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The self-assembly of the pentanuclear double helicates Hh, Ha and He from the corresponding oligobipyridine strands Lh, La and Le and Cu1 ions has been investigated by NMR and electrospray mass spectrometry (ESMS). Where as Hh is assembled rapidly (in less than 20 min), He (about 20 h) and especially Ha (about 60 h) form much more slowly. The rate decreases strongly with increasing steric bulk of the substituents in the 4,4′-positions on the bipyridine units; this indicates that the search processes (wrapping, unwrapping) that lead to the final helicate are strongly hindered by the size of the substituents. The ESMS data give information about the species present in solution under different conditions and allow the formulation of possible formation pathways, which may involve, in particular, helicates of hairpin type.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 85
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1417-1426 
    ISSN: 0947-6539
    Schlagwort(e): dendrimers ; macromolecules ; phosphorus compounds ; substitutions ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A variety of dendrimers up to generation 7 possessing terminal P(S)Cl2, (3-[G1]-3-[G7]) or P(O)Cl2, (7-[G1]-7-[G3], 7-[G3, 7-[G7) have been tri- and tetrafunctionalized. Selective monosubstitution of P(X)Cl2 (X = S, 0) termini with allylamine or propargylamine gave the trifunctionalized dendrimers 5-[G1], 5-[G7], 8-[G1], 8-[G3], 10[G1], 11-[G4], ll-[G4], 12-[G1]-12-[G3], 12-[G5], and 12-[G7]. Reaction of dendrimers 4-[G1] and 4-[G4], possessing terminal P(S)[N-allyl) fragments, with propargylamine afforded trifunctionalized dendrimers l4-[G1 and l4-[G4]. Multiply trifunctionalized macromolecules 13-[G2] and 13-[G3] with P(S)(NH-allyl)(NH-propargyl) moieties at the surface were prepared by treatment of 8-[G2] and 8-[G3] with propargylamine. Dendrimers 15-[G1]-l5-[G3] and l6-[G1]-l6-[G3] with P(O)(NH-allyl)(OC6H4CHO) and P(O)(NH-propargyl)(OC6H4CHO) termini were also synthesized. Reaction of hydrazine or cyanomethylenetriphenylphosphorane (17) with compounds 15-[G1], 15-[G3], and 16-[G1]-16-[G3] led to the multiply tetrafunctionalized dendrimers 18-[G1], 18-[G3], 19-[G1], 20-[G1]-20-[G3], 21-[G1], and 21-[G2].
    Zusätzliches Material: 3 Ill.
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  • 86
    ISSN: 0947-6539
    Schlagwort(e): aryldiamines ; chelate ligands ; organometallic compounds ; ruthenium complexes ; structure elucidation ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The new anionic functionalized aryldiamine ligands [2,6-(Me2NCH2)2-4-R-C6H2]- (R = Me3SiC≡C, C6H5, Me3-Si), formally derived from [2,6-(Me2-NCH2)2C6H3]-, have been prepared as their lithium compounds. The compound [Li{2,6-(Me2NCH2)2-4-Ph-C6H2}]2 crystallizes in the monoclinic space group C2/c (no. 15) with a = 13.1225(5), b = 13.5844(7), c = 18.9859(12) Å, β = 105.329(5)°, V = 3264.0(3) Å3. Z = 4. The structure refinement converged to R1 = 0.0374 for 2037 observed reflections [Fo〉4σ(Fo)] and wR2 = 0.0922 for 2560 unique data. The organolithium compounds have been used in transmetalation reactions to give the corresponding functionalized organoruthenium(II) complexes [RuII{2,6-(Me2NCH2)2-4-R-C6H2}-(terpy)]+Cl- (terpy = 2,2′;6′,2′-terpyridine). The RuII species with R = HC°C has also been synthesized.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 87
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1477-1482 
    ISSN: 0947-6539
    Schlagwort(e): asymmetric syntheses ; epothilones ; macrolides ; natural products ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Members of a new class of macrolide - the so-called epothilones (1) - showing a taxol-like biological activity have recently been isolated. A convergent approach to 1 is presented, and the asymmetric syntheses of the three key intermediates 3, 4, and 8 are reported.
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  • 88
    ISSN: 0947-6539
    Schlagwort(e): carbenes ; CH activation ; dinuclear complexes ; sandwich complexes ; spin equilibria ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The dinuclear μ-cyclopentadienylidene complexes [(C5R5)Co(μ-C5H4)-Co(C2H4)(C5R'5)] (5) [5aa (R = R' = H), 5ab (R = H, R' = Me), 5ac (R = H, R'5 = H4Me), 5ba (R = Me, R' = H), 5bb (R = R' = Me) and 5da (R5 = Me4Et, R' = H)] were synthesised from [(C5R5)Co(η4-C5H6)] (4) [4a (R = H), 4b (R = Me), 4d (R5 = Me4Et)] and [(C5R'5)Co(C2H4)2] (1) [1a (R' = H), 1b (R' = Me) and 1c (R'5 = H4Me)]. In these reactions, both CH bonds of the methylene group of coordinated cyclopentadiene are activated under mild conditions. Substitution of the ethylene ligand in 5 by L leads to the carbonyl, isocyanide, phosphine, and phosphite derivatives [(C5R5)Co(μ-C5H4)Co(L)-(C5R'5)] [6aa, 6ab, 6ba, 6bb (L = CO), 7aa (L = tBuNC), 8aa, 8ab (L = PMe3), 9aa (L = PMe2Ph), 10aa (L = PMePh2) and 11aa (L = P(OMe)3)]. The crystal structures of 5aa, 5ab, 5ba, 6aa and 8aa have been determined. The experimental geometry is rationalised in terms of two limiting structures with μ-η4:η1 and μ-η5:η1 coordination of the bridging cyclopentadienylidene ligand. On the basis of the 18 valence electron rule, zwitterionic character is assigned to latter. This structure is preferred when L is an acceptor ligand, as in 6. In solution, 5-11 are fluxional with rapid rotation about the very short cobalt-carbene C bond. In addition the hindered rotation of the ethylene ligand in 5ab was studied by DNMR spectroscopy. In solution, a singlet-triplet equilibrium was established by variable-temperature NMR spectroscopy for 8aa. The temperature-dependent 1H NMR line shifts were analysed by means of an isotropic shift model to give 24≤ΔH° ≤ 32 kJ mol-1 and 45≤ΔS° ≤74 J mol-1 K-1 with the triplet state being preferred by entropy at higher temperatures.
    Zusätzliches Material: 9 Ill.
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  • 89
    ISSN: 0947-6539
    Schlagwort(e): boron compounds ; fluxionality ; iron complexes ; NMR spectroscopy ; rearrangements ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The fluxional behavior of [1-4-η4 - exo - 7 - dipropylborylcyclohepta - 1,3,5-triene]tricarbonyliron (14) has been studied by dynamic NMR. The 2 D 1H and 13C EXSY NMR experiments carried out at various temperatures revealed that three independent fluxional processes occur in 14. The fastest rearrangement is a [1,7] B sigmatropic shift accompanied by [1,2] Fe migration (EA = 71.2±2.3 kJ mol-1, ln A = 32±1). Two other rearrangements also take place: [1,3] B sigmatropic and [1,3] Fe haptotropic migrations. The analysis of the observed selectivity towards [1,j] B sigmatropic shifts ([1,3] and [1,7] B shifts are observed, but [1,5] B shifts are not) in terms of theoretical predictions gives reason to assume that the [1,j] boron migrations occur with inversion of configuration at the migrating atom.
    Zusätzliches Material: 4 Ill.
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  • 90
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. cpi 
    ISSN: 0947-6539
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 91
    ISSN: 0947-6539
    Schlagwort(e): ab initio calculations ; inorganic polymers ; mechanistic studies ; titanium compounds ; titanoxanes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The controlled ionization of the linear [Cl-Ti-O-Ti-Cl] skeleton allowed the generation of the [Cl-Ti-O-Ti]+ dimer, which is nonsymmetrical as a consequence of extended Cl-Ti-O π interactions. The [Ti=O] unit thus formed is a building block for a variety of titanoxane structures. This chemistry has been investigated from a theoretical point of view by ab initio MO analysis of the [Cl-Ti-O-Ti-Cl] and [Cl-Ti-O=Ti]+ fragments. These calculations lead to the conclusion that single ionization generates the [Ti=O] unit, whereas double ionization does not affect the μ-oxo bonding mode in [Ti-O-Ti]2+ or [S-Ti-O-Ti-S]2+ (where S is a pure σ-donor ligand or solvent). This observation has been confirmed experimentally by ionizing the following model complexes: [(Cl)(acacen)-Ti-O-Ti(acacen)(Cl)] (3) (acacen = N,N'-ethylenebisacetylacetoneiminato dianion) and [(Cl)(salen)Ti-O-Ti(salen)-(Cl)] (4) (salen = N,N'-ethylenebissalicylideneiminato dianion), where the linear Cl-Ti-O-Ti-Cl unit is assured by the square-planar bonding mode of the tetradentate Schiff base ligand. The double ionization of 3 with AgNO3 gave the conventional μ-oxo derivative [(acacen)(η1-ONO2)Ti-O-Ti(acacen)(η1-ONO2)] (5). In contrast, the stepwise ionization of 3 and 4 with NaBPh4 in THF led to the nonsymmetrical [Cl-Ti-O=Ti]+ intermediates, which are the parent compounds for a variety of linear titanoxanes. The following species containing a Ti=O unit have been isolated from the NaBPh4-assisted ionization of 3: [(acacen)Ti=O-BPh3] (6) and [(L)(acacen)Ti=O-Ti(acacen)-O-(acacen)Ti-O=Ti(acacen)(L)]2+2 BPh-4 (L = THF, 7; L = none, 8). The same reaction carried out on 4 led to [(THF)-(salen)Ti=O - Ti (salen) - O - (salen)Ti-(THF)]2+2 BPh-4 (9) and [(L)(salen)-Ti=O-Ti(salen) - O - (salen)Ti-O=Ti-(salen)(L)]2+ 2BPh-4 (L = THF, 10; L = Py, 11; L = none, 12, polymeric form). A scheme is proposed to explain the formation of the species derived from the single ionization of 3 and 4, where the origin and the binding properties of the [Ti=O] unit play a major role.
    Zusätzliches Material: 7 Ill.
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  • 92
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996) 
    ISSN: 0947-6539
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 93
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1493-1497 
    ISSN: 0947-6539
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 94
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1499-1504 
    ISSN: 0947-6539
    Schlagwort(e): charge ordering ; giant magnetoresistance ; magnetoresistance ; manganates ; rare earth manganates ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The discovery of giant magnetoresistance (GMR) in rare earth manganates of the general formula Ln1-xAxMnO3 (Ln=rare earth, A=divalent cation) has aroused much interest not only because of its technological implications, but also due to the fascinating features and mechanism of the phenomemon in these oxides. GMR is observed in these manganates when they become ferromagnetic and transform from an insulating state to a metallic state close to the Curie temperature. The essential features of magnetoresistance in the manganates can be understood on the basis of the double-exchange mechanism, but this is too simplistic to account for all the observed data. The most curious property of the manganates relates to the high resistivity exhibited in the so-called metallic state. Charge ordering competes with the double-exchange interaction responsible for ferromagnetism and GMR in these materials. The charge-ordered (charge-crystal) insulating state in the rare earth manganates can be melted into a metallic and ferromagnetic charge-liquid state by applying a magnetic field, thus providing a unique case of charge and spin separation in solids. The observation of GMR in Tl2Mn2O7 shows that there can be causes other than double-exchange for the phenomenon.
    Zusätzliches Material: 12 Ill.
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  • 95
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 1505-1508 
    ISSN: 0947-6539
    Schlagwort(e): enol ethers ; phosphatidylcholine ; plasmenyl phospholipids ; total syntheses ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The first practical total chemical synthesis of a plasmenylcholine (1-O-1'-(Z)-hexadecenyl-2-hexadecanoyl-sn-glycero-3-phosphocholine) with pure (Z) olefin stereochemistry is reported. Monopalmitin was doubly protected as the 3-TBDPS-2-TBDMS ethers (tert-butyldiphenylsilyl-, tert-butyldimethylsilyl-) and converted to the corresponding 1-O-1′-(Z)-hexadecenyl-2-TBDMS-3-TBDPS-glyceryl ether (by the method of ref. [43]). Clean deprotection with tetra-butylammonium fluoride in the presence of imidazole gave 1-O-1′-(Z)-hexadecenylglycerol in 〉90% yield. Resilylation with TBDPSCl followed by acylation of the sn-2 alcohol with palmitoyl chloride and deprotection of the resulting 3-TBDPS-2-hexadecanoyl-1-O-1′-(Z)-hexadecenylglycerol at -20°C with Bu4NF gave 2-hexadecanoyl-1-O-1′-(Z)-hexadecenylglycerol in 86% yield. The 3-phosphocholine group was attached by phosphorylating the free hydroxyl with 2-chloro-2-oxo-1,3,2-dioxaphospholane in the presence of pyridine, instead of Et3N, as base to avoid acyl migration; the dioxaphospholane triester intermediate was subsequently cleaved with Me3N to give 1-O-1′-(Z)-hexadecenyl-2-hexadecanoyl-sn-glycero-3-phosphocholine in 18% overall yield from monopalmitin. The efficiency and flexibility of this route makes it well-suited to the preparation of a wide variety of 1-, 2-, and 3-substituted as well as isotopically labeled plasmenylcholines for biophysical and biochemical studies.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 96
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 3-3 
    ISSN: 0947-6539
    Schlagwort(e): Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 97
    ISSN: 0947-6539
    Schlagwort(e): density-functional theory ; NMR chemical shifts ; pseudopotentials ; relativistic effects ; transition-metal complexes ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Carbon and oxygen NMR chemical shift tensors for Group 6 hexacarbonyl complexes M(CO)6 (M = Cr, Mo, W) have been calculated by using a combination of quasirelativistic metal effective-core potentials and density-functional theory. Comparison with high-resolution solid-state shift tensors indicates excellent agreement between theory and experiment. The sensitivity of the shifts to the W-C distance in W(CO)6 is discussed. A breakdown of the shielding tensor components into contributions from localized molecular orbitals allows the detailed interpretation of the trends on going down Group 6, and of differences to free CO. Group trends in the carbon shielding tensors are related largely to contributions from M-C σ-bonding orbitals. The presence of occupied metal (n-1)p and (n-1)d orbitals is partly responsible for the changes on going from free to metalbound CO. The origin of the less pronounced trends in the oxygen shielding tensors is more complicated. The influence of scalar relativistic effects on the shift tensors has been studied for W(CO)6 and is found to be relatively small, in spite of considerable changes in the W-C distance.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 98
    ISSN: 0947-6539
    Schlagwort(e): catenanes ; polycatenanes ; polyrotaxanes ; rotaxanes ; self-assembly ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The self-assembly of three bis[2]catenanes and a bis[2]rotaxane, by two complementary strategies, is reported. A synthetic route to derivatives of bis-para-phenylene[34]crown-10 (BPP34C10) and 1,5-naphtho-para-phenylene[36]-crown-10 (1/5NPP36C10) containing a fused five-membered ring with a secondary amine function is described. These intermediate N-allylimido macrocyclic polyethers undergo template-directed reactions with 1,1′-[1,4-phenylenebis-(methylene)]bis-4,4′-bipyridinium bis-(hexafluorophosphate) and 1,4-bis(bromo-methyl)benzene to produce [2]catenanes containing an N-allyl functionality. The N-allylimido macrocyclic polyethers have also been reduced and deprotected to afford macrocycles possessing a free NH group, which are then linked through a 4,4′-biphenyldicarbonyl spacer to produce bis(crown ether)s, in which each crown ether moiety has two recognition sites. These ditopic BPP34C10 and 1/5NPP36C10 derivatives are capable of sustaining self-assembly reactions at both recognition sites to yield bis[2]catenanes. The self-assembly of a complementary bis[2]catenane, in which two tetracationic cyclophanes are linked together with a flexible hexyl chain, has also been achieved by treating 1,1′-[1,4-phenylenebis(methylene)]bis-4,4′-bipyridinium bis-(hexafluorophosphate) with a compound containing two linked 1,4-bis(bromomethyl)benzene units in the presence of BPP34C10. Replacing BPP34C10 with a dumbbell-shaped compound containing a linear polyether unit intercepted by a naphthalene residue and terminated by two bulky adamantoyl groups has led to the self-assembly of a bis[2]rotaxane. The X-ray crystal structures of one of the catenanes and its associated crown ether component are reported, together with solution state dynamic 1H NMR spectroscopic studies, showing that there is substantial degree of order characterizing the molecular structure of the catenanes.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 99
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 2 (1996), S. 83-87 
    ISSN: 0947-6539
    Schlagwort(e): enzyme models ; iron complexes ; molybdenum complexes ; nitro genase ; semi-empirical calculations ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A model for the active site of nitrogenase is suggested and examined by means of the intermediate neglect of differential overlap (INDO) quantum mechanical method. The initial steps of the nitrogen fixation process are discussed within the framework of the present model, and it is shown that of several binding sites, initial location of the nitrogen molecule inside the MoFe cofactor is favored. Possible pathways for electron and proton delivery to the active site are also suggested on the basis of electrostatic potential calculations.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 100
    ISSN: 0947-6539
    Schlagwort(e): ab initio calculations ; cyclic ylides ; heterocycles ; phosphorus ylides ; Chemistry ; General Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A number of possible strategies for the preparation of λ5-phosphetes were tested as follows: cyclopropenium 6 was treated with the lithium salt of diphenylphosphine to give phosphinocyclopropene 7, but 7 did not undergo ring expansion upon photolysis or thermolysis. P-chloro-C—trimethylsilyl-substituted ylide 8b reacted with two equivalents of dimethyl acetylenedicarboxylate to afford phosphinine 13 via a transient λ5-phosphete 12. Addition of aluminum trichloride to P-halogenated ylides 17a-b led to dihydrophosphetium salts 19a-b, which, upon treatment with pyridine, isomerized into the 1, 2-dihydrophosphet-2-ium salts 20a-b. Hydrolysis of derivatives 20a-b cleanly afforded phosphoniums 21 a-b, which reacted with NaN(SiMe3)2 to give rise to the corresponding λ5-phosphetes 22a-b. The benzo-λ5-phosphete 22a underwent ring expansion reactions with dimethyl acetylenedicarboxylate and acetonitrile, leading to benzo-λ5-phosphinine and benzo-1, 4λ5-azaphosphinine in good yields. Derivative 22b was characterized by X-ray crystal structure analysis. Ab initio SCF calculations, IGLO-13C chemical shifts and Δχ for various benzannulated derivatives and phosphorus heterocycles are presented.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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