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  • General Chemistry  (1,786)
  • Inorganic Chemistry  (605)
  • Fisheries
  • 2015-2019  (17)
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  • 2015-2019  (17)
  • 2000-2004
  • 1995-1999  (2,390)
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  • 1940-1944
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  • 1
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    Status of fish Consumption per capita of Tehran citizens (2017)
    Details
    Publication Date: 2021-05-19
    Description: Status of fish consumption was analyzed by completing the 295 questionnaires in all 22 metropolitan regions of Tehran from different households in 2008. After reviewing the descriptive and statistics analysis along with the non-parametric statistics, the fish consumption per capita was extracted through formulas. The average and mode of purchasing of each household occurs 11 times per year with 5.1 Kg in each time. Considering the higher fish consumption growth rate in Iran, the sequence of interest in all kinds of protein is as follows: poultry, mutton, beef, Trout, wild fishes and Chinese carps. The highest interest of households to buy fish more than other protein resources is due to the nutrient value of it. An average of 33.2% purchasing is dedicated to the farmed fish. 59% of purchasers are interested to buy packed up fish products and pay attention to the label of nutrient values on the product package. Fish consumption per capita is 13.3 Kg, which is divided to 6.4 kg for farmed fishes, 5.8 Kg for wild fishes and 1.1 Kg for canned fish. The higher consumption per capita of Tehran citizens in comparison with other people from other cities, who are living in Tehran, is because of their tendency and freshness of farmed fishes. In contrast, the consumption of canned and wild fishes among people of littoral regions who live in Tehran is higher than others.
    Description: Published
    Keywords: Fish consumption per capita ; Fish ; Consumption ; Per capita ; Fisheries
    Repository Name: AquaDocs
    Type: Journal Contribution , Refereed
    Format: pp.546-556
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  • 2
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    Entrepreneurship development; a step towards achieving the economic and social goals of fisheries: (Explanation and ranking of effective environmental factors using fuzzy Delphi and FAHP approach) (2017)
    Details
    Publication Date: 2021-05-19
    Description: The purpose of the present research was to identify and rank the effective environmental (background) indices on OE process in Mazandaran Fisheries Organization. In terms of data collection, the method used in this study was the descriptive-survey method and in terms of research purposes, it was an applied research. Statistical population included experts and leading experts of Mazandaran fisheries organization in 2014. After literature review, the effective environmental (background) indices on OE were identified. Data were collected using Delphi and paired comparisons questionnaires, and analyzed using fuzzy Delphi method and FAHP. The results showed that the effective environmental (background) indices on OE, in order of priority, were the economic environments, legal-political environment, social-cultural environment, technological environment, administrative environment and international environment.
    Description: Published
    Keywords: Development ; Economic ; Environmental ; Organizational Entrepreneurship ; Fuzzy Delphi ; Fuzzy AHP ; Mazandaran Fisheries Organization ; Entrepreneurship ; Fisheries ; Explanation ; Ranking ; Factors
    Repository Name: AquaDocs
    Type: Journal Contribution , Refereed
    Format: pp.125-138
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  • 3
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    Creation and promotion Iranian fisheries research institute laboratories data base (2017)
    Details
    Publication Date: 2021-05-19
    Description: Creating a database of affiliated laboratories of the institute is organized with the aim of integrating information related to laboratories of research centers and their subsidiaries. The main objective of conducting this project in this stage is to upgrade it, establish and running one software system based on up-to-date technology of networking. For this purpose organizing the centers database, a periodic report on various aspects can be done which help for implementing appropriate monitoring and management .Among the sectors that are designed and upgraded for this system include : Portal, bank of information, advanced possibilities for inputting data, searching and reporting on laboratory.The advantages of this precise and updated reports can be collected easily from the general information of research institutes and centers, reports of the number of lab experts with different educational levels in affiliated centers, awareness of numbers and status of the chemical materials in the laboratories of each center, and the significant and important point is about economizing equipment, chemical materials and on time calibration.
    Description: Published
    Keywords: Bank of information ; Laboratories ; Research institute ; Network ; Data ; Fisheries
    Repository Name: AquaDocs
    Type: Journal Contribution , Refereed
    Format: pp.149-153
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  • 4
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    Study of barriers and strategies for development of ornamental fish industry in Iran “case study of Markazi Province” (2017)
    Details
    Publication Date: 2021-05-19
    Description: Caspian Sea, Persian Gulf and the natural aquatic environment, made Iran’s geo-strategic and socioeconomic situation of the fisheries and aquaculture sector unique. This sector in the three areas of “ecotourism”, “food production” and “social behavior” play a crucial role in achieving Iran's Vision Policy of 1404 goals. However, Iran's valuable position in ornamental fish farming industry has been less attention and several issues challenged its development trend. Markazi is one of the leading provinces in this industry. So the main purposes of research were to identify current situation and providing development strategies. This study was descriptive and data were collected by survey method. The Statistical population was ornamental fish’s Producers and experts in Markazi province which due to limit number, census sampling was applied. The main tool for gathering information was questionnaire which its face validity confirmed through educational specialist and expert’s viewpoint. Also, the reliability of research tool was evaluated by Coronbach Alfa Test. The results showed that "Employment and income" and "Interest in breeding ornamental fish" were two main reasons to attract practitioners to this industry. The respondents considered the current situation ornamental fish industry, undesirable (Score 1.17 out of 5). Factor analysis showed that five factors named; "Corporate management and food resources", "management of extension and informing about authentic breeding principles", "Care Management and Insurance", "imported fish quality management" and "technical and financial support" have explained about 80% of the variance of the current situation and barriers to the development of ornamental fish industry in Markazi Province. The most important strategies to reduce facing problem in mentioned industry were development priority belonged ornamental fish industry trade system and development of specialized human resources training.
    Description: Published
    Keywords: Ornamental fish industry ; ِDevelopment ; Ornamental ; Fish ; Industry ; Fisheries ; Aquaculture ; Quality
    Repository Name: AquaDocs
    Type: Journal Contribution , Refereed
    Format: pp.133-148
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  • 5
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    Evaluación de la pesquería de langosta Panulirus argus (Decapoda: Palinuridae) en la plataforma noroccidental. (2017)
    Details
    Publication Date: 2021-05-19
    Description: Debido a la disminución de las poblaciones de Panulirus argus a nivel nacional, y al conocimiento limitado sobre su estado actual en la región noroccidental de Cuba, se realizó la evaluación de la pesquería de langosta en esta zona. Se aplicó un Modelo Dinámico de Biomasa basado en series de captura (t) y esfuerzo pesquero (días pesca) por temporadas de pesca entre 1955-2015. El modelo mostró buen ajuste a los datos de captura (R2 = 0,74). Los parámetros estimados fueron: coeficiente de capturabilidad (q = 6,08 x 10-5), tasa intrínseca de crecimiento de la población (r = 0,18) y capacidad de carga del ambiente (K = 5 621 t). La captura máxima sostenible (CMS) obtenida fue de 251 t con un esfuerzo (fCMS) de 1 469 días pesca, una tasa de mortalidad por pesca (FCMS) de 0,089 y una biomasa (BCMS) de 2 811 t. A partir de 2012 se observó un incremento en la captura por unidad de esfuerzo, lo cual puede reflejar una cierta recuperación de la abundancia de la especie, ya que la biomasa presenta una tendencia creciente desde 2005 aunque todavía se encuentra por debajo del límite de sostenibilidad (BCMS), por lo que el recurso se califica como agotado. Los resultados de la tasa de mortalidad por pesca (F) muestran que existieron niveles elevados de explotación en los períodos 1966-1978, 1982-1992 y 1994-2005, que contribuyeron con la disminución de la biomasa por debajo de su nivel sostenible desde 1972. Sin embargo, en los últimos años se observa una reducción de F por debajo del límite de FCMS, y por lo tanto la pesquería no se encuentra bajo efectos de sobrepesca desde 2005.
    Description: Due to the declining populations of Panulirus argus nation wide, and the limited knowledge about its current status in the northwestern region of Cuba, an assessment of the spiny lobster fishery in this area was conducted. A biomass dynamic model was applied, based on catch series (t) and fishing effort (fishing days) by fishing seasons between years 1955-2015.The model showed good fit to the data catch (R2 = 0,74).The estimated parameters were: catchability coefficient (q = 6,08 x 10-5), population growth intrinsic rate (r = 0,18) and environment carrying capacity (K = 5 621 t). The maximum sustainable yield (MSY) obtained was 251 t, with an effort (fMSY) of 1 469 fishing days, a fishing mortality rate (FMSY) of 0.089 and a biomass (BMSY) of 2811 t. From 2012 an increase in catch per unit effort was observed, which may reflect a recovery in the abundance of the species. The biomass also shows a rebuilding from 2005, but remains depleted below the limit of BMSY. The fishing mortality rate (F) was high in the periods 1966-1978, 1982-1992 and 1994-2005, which contributed to the decline of the biomass below its sustainable level since 1972. In recent years F decreased bellow FMSY and therefore there is not overfishing since 2005.
    Description: Published
    Keywords: Langosta ; Modelo dinámico de biomasa ; Panulirus argus ; Pesquería ; Región noroccidental ; Lobster ; Biomass dynamic model ; Fisheries ; Northwestern region
    Repository Name: AquaDocs
    Type: Journal Contribution , Refereed
    Format: pp.24-29
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  • 6
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    Fishing pattern, maximum constant yield (MCY) and recruitment pattern of Thunnus tonggol in Hormuzgan province (2017)
    Details
    Publication Date: 2021-05-19
    Description: Thunnus tonggol is one of the most important large pelagic fish species in Hormuzgan province waters. Nominal catch of T. tonggol in 2010 was 32405 tones comprising 65% of total catch of large pelagic fishes. For sustainable exploitation of the resources of this fish, we need to identify its fishing pattern, maximum constant yield and recruitment pattern. Hence, length and weight data were collected randomly from 6 major artisanal fish-landing sites Hassineh, Kong, Bandar Abbas, Salakh, Sirik and Jask in Hormuzgan province, starting in April 2010 over one year. Growth parameters L∞ and K were estimated at 112.23cm 0.3 and (1/year), respectively. Hence, the natural mortality was calculated at 0.43 (1/year) and the maximum constant yield was computed at 11880 tones. Length-weight power relationship, W= aFLb , was W= 3×10-05FL2.82 that showed T. tonggol have isometric growth. Fishing pattern indicated that almost 85% of the catch was under the size at first maturity. Maximum recruitment pattern was in November with average fork length being 27cm. For optimum exploitation of T. tonggol stocks, we suggest two approaches including fishing ban in the maximum recruitment time and gear (Drift gillnet) modification.
    Description: Published
    Keywords: Mackerels ; Thunnus tonggol ; MCY ; Fishing ; Pattern ; Fisheries ; Fish ; Fish stocks
    Repository Name: AquaDocs
    Type: Journal Contribution , Refereed
    Format: pp.129-138
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  • 7
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    Structure of macrobenthic invertebrate population in the southern coast of Caspian Sea for fish cage culture establishment (2017)
    Details
    Publication Date: 2021-05-19
    Description: Published
    Keywords: Establishment ; Streblospio gynobranchiata ; Cerastoderma glaucum ; Fish cage culture ; Structure ; Macrobenthic ; Invertebrate ; Population ; Culture ; Fish ; Biomass ; Abundance ; Feeding ; Fisheries
    Repository Name: AquaDocs
    Type: Journal Contribution , Refereed
    Format: pp.23-40
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  • 8
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    Effects of commercial fishing on adult Atlantic salmon (Salmo salar) in a Quebec river (2017)
    Woods Hole Oceanographic Institution
    Details
    Publication Date: 2022-05-25
    Description: Despite an absence of freshwater exploitation, the adult salmon run in the Matamek River, Quebec, declined during 1975-1980 to 〈23% of the level thought to occur there prior to 1967. Returns in 1979 and 1980 of adults tagged as smolts were 1.0% and 0.9%, respectively. Numbers of emigrating smolts and their corresponding adult returns are not significantly correlated, although we observed a trend towards more salmon (2 sea year fish) returning with larger numbers of migrating smolts. Since 1967 there is noted a decrease in the age at which returning adults smolted and females appear to now constitute a larger percentage of returning grilse and salmon. These, and other changes in life history characteristics, appear to be caused solely by commercial exploitation.
    Description: Prepared by the Woods Hole Oceanographic Institution and the Department of Recreation, Fish and Game of the Province of Quebec.
    Keywords: Atlantic salmon ; Fish populations ; Atlantic salmon ; Fisheries
    Repository Name: Woods Hole Open Access Server
    Type: Technical Report
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  • 9
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    Fishy Business: Fish in the United States Serial Set (2017)
    IAMSLIC
    Details
    Publication Date: 2022-05-25
    Description: The United States Congressional Serial Set contains a wide variety of historical documents relating to natural resources and their history in the United States. It is an excellent resource for those researching historical data concerning fisheries, from extant species and ecology to economic issues. Information on resources outside the United States is also available due to the U.S. history of explorations and expansions. Charts, maps and tables are found within many of the papers and reports. There are also numerous scientific illustrations.
    Keywords: Fisheries ; fisheries data ; historical account ; United States government data ; United States Serial Set
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 10
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    Lutjanus ehrenbergii (2017)
    University of Tehran , Kish International Campus | Iran, Kish Island
    Details
    Publication Date: 2021-05-19
    Description: Unpublished
    Keywords: Lutjanus ehrenbergii ; Fish ; Fisheries
    Repository Name: AquaDocs
    Type: Images/Video , Non Refereed
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  • 11
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    Habitats and Biota of the Gulf of Mexico: Before the Deepwater Horizon Oil Spill. Volume 2: Fish Resources, Fisheries, Sea Turtles, Avian Resources, Marine Mammals, Diseases and Mortalities. (2017)
    Springer Open | New York, USA
    Details
    Publication Date: 2021-05-19
    Description: The Deepwater Horizon accident and oil spill in the Gulf of Mexico from the Macondo well began on April 20, 2010. Oil flowed into the Gulf for 87 days until the well was capped on July 15, 2010, and declared sealed on September 19, 2010. The United States (USA) Government initially estimated that a total oil discharge into the Gulf of 4.9 million barrels (210 million U.S. gallons) resulted from the spill; however, the estimate was challenged in litigation, reduced to 3.19 million barrels by a trial court, and remains in dispute. A massive cleanup, restoration, and research program followed and continues to the present, mostly funded by BP Exploration & Production Inc. (BP).
    Description: Published
    Keywords: Deepwater Horizon Oil Rig ; Pollution effects ; Fish ; Fisheries ; Oil spills ; Marine mammals ; Birds ; Turtles ; Diseases
    Repository Name: AquaDocs
    Type: Book/Monograph/Conference Proceedings , Refereed
    Format: lxv, pp.869-1757
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  • 12
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    Ecsenius pulcher (2017)
    University of Tehran , Kish International Campus | Iran, Kish Island
    Details
    Publication Date: 2021-05-19
    Description: Unpublished
    Keywords: Ecsenius pulcher ; Blenny ; Fish ; Fisheries ; Coral reef ; Benthic
    Repository Name: AquaDocs
    Type: Images/Video , Non Refereed
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  • 13
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    Usinas hidrelétricas no rio Paraná : insustentabilidade e exclusão social em populações tradicionais de Ituzaingó (Corrientes, Argentina) e Porto Rico (Paraná, Brasil). (2017)
    Universidade Estadual de Maringá. Departamento de Biologia. Programa de Pós-Graduação em Ecologia de Ambientes Aquáticos Continentais.
    Details
    Publication Date: 2022-07-12
    Description: The promotion of mega-constructions, as reservoirs of Itaipu and Yacyretá, are based in ideas of development and progress. However, the report showed by the World Commission on Dams (WCD) in November of 2000, made responsible to the big reservoirs, the projects on Sustainable Regional Development (SRD), as generating of social and environmental damages. Thus, the main goal of the present study is to investigate the social and cultural transformations in the communities of the islanders and riparian people from Ituzaingó and Porto Rico with the constructions of the hydroelectric power plants of Itaipu (Brazil), Porto Primavera (Brazil) and Yacyretá (Argentina). Are analyzed many factors that allowed the built of those reservoirs and their principal actors. Also, the contradictions more visible verified in the social community and environmental of Ituzaingó and Porto Rico. The three reservoirs are located on the Paraná River basin, because the exploration of there hidroelectrical potential and promote of development of the different regions. Although, the reservoirs of Itaipu and Yacyretá, as projects of DRS, not allowed better social conditions for the traditional communities of Porto Rico and Ituzaingó, and they were made loose their significance when they are compare with the damages caused. In the other hand, its main beneficiaries are the multilateral financiers agencies and the economical trusts with distant headquarters from the south of Brazil and the northeast of Argentina.
    Description: A aceitação e promoção de megaobras, como as barragens de Itaipu e Yacyretá, são baseadas em idéias de desenvolvimento e de progresso. Contudo, o informe apresentado pela Comissão Mundial de Represas (CMR) em novembro de 2000, responsabilizou às grandes represas, os projetos de Desenvolvimento Regional Sustentável (DRS) por excelência, como geradoras de uma série de danos sociais e ambientais. Destarte, o objetivo do presente trabalho foi o estudo das transformações sociais ocorridas nas comunidades de ilhéus e ribeirinhos de Ituzaingó e Porto Rico a partir das mudanças na paisagem ecológica decorrentes das construções das usinas hidrelétricas de Itaipu (Brasil), Porto Primavera (Brasil) e Yacyretá (Argentina). Com essa finalidade foram analisados alguns dos fatores que possibilitaram a concretização desses projetos assim como a identificação dos seus principais protagonistas. O trabalho também contemplou o resgate das vozes dos pescadores-lavradores da região. As três usinas assentam-se sobre o rio Paraná com o propósito de explorar o seu potencial hidrelétrico e estimular o desenvolvimento das respectivas regiões. Porém, as represas de Itaipu, Porto Primavera e Yacyretá, como projetos de DRS, não promoveram, até hoje, melhoras significativas para as comunidades tradicionais de Porto Rico e Ituzaingó. O desenvolvimento alcançado perde toda importância quando comparado aos prejuízos ocasionados. Paradoxalmente, os seus principais beneficiários são as agências financiadoras multilaterais e os consórcios econômicos com sedes distantes do sul brasileiro e do nordeste argentino.
    Description: PhD
    Keywords: Hydroelectric ; Impact environment ; Fisheries ; Paraná River ; Environment police ; Ciências Ambientais ; Brazil ; Comunidades ; Pescadores ; Política ambiental ; Exclusão social ; Ecologia humana ; Usinas hidrelétricas ; Impacto socioambiental ; Human ecology ; Brasil ; Comunity ; Paraná, Rio
    Repository Name: AquaDocs
    Type: Thesis/Dissertation
    Format: 137pp.
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  • 14
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    Final report : Market-based incentives to reduce fisheries bycatch (2017)
    Woods Hole Oceanographic Institution
    Details
    Publication Date: 2022-05-26
    Description: This report represents a first step at considering the potential for the use of market-based incentives to aid in the resolution of fishery bycatch problems. Market-based incentives have several advantages over more traditional command-and-control approaches, including cost-effective allocations of environmental controls; incentives for firms to seek technological solutions; flexibility; returns to the public for the use of its resources; and lower administrative costs in some cases. Notwithstanding these advantages and with several notable exceptions, market-based incentives are almost never employed in the management of fishery bycatch problems. There may be several reasons why this is the case, including significant distributional effects, high costs of monitoring and enforcement, difficulties in educating consumers about product attributes, administrative and transactions costs, or merely oversight. We consider this report to be an "advanced outline" of the issues surrounding the consideration of market-based incentives. We begin first by developing in Section 2 a definition of bycatch, including a "typology" of bycatch types. Next, we compile available public information on bycatch in U.S. fisheries, as defined by target species, location, and gear type (Section 3 and Appendix 1). We then review, in Section 4, two potentially relevant strands of literature, the economic theory of multispecies fisheries and studies from other social sciences of how small-scale fisheries deal with problems of bycatch. In Section 5, we describe, in general, the kinds of market-based policy instruments that may be of use in managing bycatch problems. Following this evaluation, we identify and discuss, as case studies; three priority fisheries: th~ northeastern groundfish fishery; the Gulf of Mexico shrimp fishery; and the eastern tropical Pacific yellowfin tuna fishery (Section 6). Finally, in Section 7, we outline approaches to identifying appropriate policy instruments, including a qualitative comparison of market-based approaches, an examination of the effect of specific types of uncertainty on the choice between taxes and ITQs, and the development of a "proposal" for a bycatch management "policy package." This section concludes with a proposal for a set of priority market-based approaches to bycatch management in the three cases discussed in Section 6.
    Description: NOAA Contract No. 50-DGNF-5-00172
    Keywords: Bycatch ; Fisheries
    Repository Name: Woods Hole Open Access Server
    Type: Working Paper
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  • 15
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    [Editors' Choice] Fluorine frolicking with eight friends (2017)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2017-02-10
    Description: Author: Jake Yeston
    Keywords: Inorganic Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
    Published by American Association for the Advancement of Science (AAAS)
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  • 16
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    [This Week in Science] A salty route to an all-nitrogen ring (2017)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2017-01-27
    Description: Author: Jake Yeston
    Keywords: Inorganic Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 17
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    [Perspective] Polynitrogen chemistry enters the ring (2017)
    American Association for the Advancement of Science (AAAS)
    In: Science
    Details
    Publication Date: 2017-01-27
    Description: Polynitrogens have the potential for ultrahigh-performing explosives or propellants because singly or doubly bonded polynitrogens can decompose to triply bonded dinitrogen (N2) with an extraordinarily large energy release. The large energy content and relatively low activation energy toward decomposition makes the synthesis of a stable polynitrogen allotrope an extraordinary challenge. Many elements exist in different forms (allotropes)—for example, carbon can exist as graphite, diamond, buckyballs, or graphene. However, no stable neutral allotropes are known for nitrogen, and only two stable homonuclear polynitrogen ions had been isolated until now—namely, the N3− anion (1) and the N5+ cation (2). On page 374 of this issue, Zhang et al. (3) report the synthesis and characterization of the first stable salt of the cyclo-N5− anion, only the third stable homonuclear polynitrogen ion ever isolated. Author: Karl O. Christe
    Keywords: Inorganic Chemistry
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Geosciences , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 18
    Electronic Resource
    Electronic Resource
    Impact of water control projects on fisheries resources in Bangladesh (1996)
    Springer
    Environmental management 20 (1996), S. 523-539 
    Details
    ISSN: 1432-1009
    Keywords: Water control ; Floodplain ; Fisheries ; Bangladesh ; Chandpur
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01474653
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  • 19
    Electronic Resource
    Electronic Resource
    Fish communities in the African Great Lakes (1996)
    Springer
    Environmental biology of fishes 45 (1996), S. 219-235 
    Details
    ISSN: 1573-5133
    Keywords: Ecology ; Behaviour ; Evolution ; Cichlids ; Fisheries ; Conservation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: 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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00003090
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  • 20
    Electronic Resource
    Electronic Resource
    Masthead (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961290101
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  • 21
    Electronic Resource
    Electronic Resource
    Triferriothioxophosphoranes: First Structural Characterization of a μ3-P=S ComplexDedicated to Prof. Dr. M. Herberhold on the occasion of his 60th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 11-13 
    Details
    ISSN: 0009-2940
    Keywords: Triferriophosphane sulfide ; Metallothioxophosphorane ; PS complex ; Spiro compounds ; Decarbonylation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The P-H-functional triferriophosphonium salts [{CpFe-(CO)2}3PH]2FeCl4 (1) and [{μ-CO(CpFeCO)2}{CpFe-(CO)2}PH]2FeCl4 (4) are easily deprotonated by DBU to the corresponding unstable triferriophosphanes 2, 5, which subsequently are oxidized by sulfur to the triferriophosphane sulfides {CpFe(CO)2}3P=S (3) and {μ-CO(CpFeCO)2}{CpFe-(CO)2}P=S (6), respectively. The photolysis of 3 results only in its decomposition by elimination of [CpFe(CO)2]2, whereas the photolysis of 6 cleaves off one CO ligand to give the new spiro compound (CpFeCO)(μ-η2-PS){μ-CO(CpFeCO)2} (7), where the P=S unit is η2-bonded to the 15-electron CpFeCO fragment, and the phosphorus atom bridges two 17-electron fragments. Compound 7 shows a new coordination mode of the PS unit where sulfur is also bound to one of the metal atoms. Compounds 6 and 7 can be regarded as first examples of a new class of PS complexes of transition metals. All compounds were characterized by IR, 31P{1H}- and 13C{1H}-NMR spectroscopy as well as mass spectrometry; for 6 the X-ray analytical data are given.
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    The Chemistry of 1,3,5-Triazacyclohexane Complexes, 3Part 2: Ref.. High Yield Synthesis of [Cr{N(SiMe3)2}3] and Accurate Structure Determination by Cocrystallization with Me6Si2 (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 25-27 
    Details
    ISSN: 0009-2940
    Keywords: Triazacyclohexanes ; Chromium complexes ; Amides ; Hexamethyldisilane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of N,N′,N′′-trimethyl-1,3,5-triazacyclohexane chromium trichloride ((Me3TAC)CrCl3, 1) with LiN(SiMe3)2 or NaN(SiMe3)2 in petroleum ether yields nearly quantitatively [Cr{N(SiMe3)2}3] (2) with loss of the Me3TAC ligand. Compound 2 could be crystallized from hexamethyldisilane as [Cr{N(SiMe3)2}3] · (Me6Si2)0,5 which allowed the refinement of the X-ray crystal structure in the trigonal space group P-31c (no. 163) (a = 16.012(3) Å, c = 8.4796(12) Å, V = 1882.8(6) Å3, Z = 2) without severe disorder.
    Additional Material: 3 Ill.
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    Synthesis of Novel Tridentate N,O,S and N,N,O Ligands of the Tripod Type in Racemic and Enantiomerically Pure Form (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 59-68 
    Details
    ISSN: 0009-2940
    Keywords: Glyceraldehyde ; Ligands, tridentate ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of seven chiral, tripodal N,O,S and N,N,O ligands were prepared in which N stands for a secondary amine or imidazole donor, O for a phenol, and S for a thioether or thiol metal-binding group. Key steps are (1) the construction of ortho-hydroxyacetophenones bearing the phenolic binding group and either a thioether, a protected thiol or an imidazole substituent in the α-position, and (2) subsequent reductive amination with a primary amine. The modular synthesis allows a rapid construction of a variety of structurally related ligands. In three cases, the enantiomers of the racemic products could be separated after condensation with (R)-glyceraldehyde acetonide as chiral auxiliary. The relative configurations of the cyclic N,O- and N,N-acetals thus obtained were established by NOE spectroscopy. X-ray structural analysis of two crystalline N,O- and N,N-acetals allowed the assignment of absolute configurations. Hydrolysis of the dia-stereomerically pure acetals afforded the enantiomerically pure ligands in high yield. By comparison of their CD spectra, absolute configuration could also be assigned to the third pair of enantiomerically pure ligands.
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    Kinetic Investigations of the Hydrogenation of Diolefin Ligands in Catalyst Precursors for the Asymmetric Reduction of Prochiral Olefins, II[1] (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 85-89 
    Details
    ISSN: 0009-2940
    Keywords: Rhodium complexes, chiral ; Hydrogenation ; Bisolefins ; Thermodynamic stability ; Kinetic control ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Asymmetric hydrogenations of prochiral olefines by means of chiral rhodium(I) complexes of the type [Rh(L)(PP*)]A (L = COD, [(Z,Z)-cycloocta-1,5-diene], or NBD (norborna-2;5-diene), PP* = chiral bisphosphane forming seven-membered chelate rings, A = anion like BF4-) are often associated with induction periods caused by partial blocking of the catalyst. NBD complexes are hydrogenated faster than the corresponding COD complexes. Catalytic hydrogenation of COD/NBD mixtures and the determination of the ratio of the Michaelis constants showed that the steady-state concentration of the COD complex under hydrogen is higher than that of the NBD complex. However, under argon the NBD complex predominates owing to its higher thermodynamic stability compared with that of the COD complex as determined by 31P-NMR spectoscopy. This complete reversion of the ther-modynamically determined ratios of COD to NBD complex concentration under hydrogenation conditions was proven by means of UV/Vis spectroscopy.
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    URL: http://dx.doi.org/10.1002/cber.19961290117
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    1-Bromo-3,5-bis(trifluoromethyl)benzene: A Versatile Starting Material for Organometallic Synthesis (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 233-235 
    Details
    ISSN: 0009-2940
    Keywords: Positional selectivity ; Bromination ; Halogen/lithium exchange ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-Bromo-3,5-bis(trifluoromethyl)benzene (1) can be selectively prepared by treatment of 1,3-bis(fluoromethyl)benzene with N,N'-dibromo-5,5-dimethylhydantoin in strongly acidic media. A number of synthetically useful reactions via 3,5-bis(trifluoromethyl)phenylmagnesium, -lithium, and -copper intermediates were accomplished.
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    URL: http://dx.doi.org/10.1002/cber.19961290219
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    Lithiierte Phosphanimine. Synthese und Kristallstrukturen von [LiCH2PMe2NSiMe3]4 und [LiCMe2P(iPr)2NSiMe3]2 (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 253-257 
    Details
    ISSN: 0009-2940
    Keywords: Lithiated phosphane imines ; Phosphane imines, lithiated ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Lithiated Phosphane Imines. Synthesis and Crystal Structures of [LiCH2PMe2NSiMe3]4 and [LiCMe2P(iPr)2NSiMe3]2The title compounds were prepared by the reaction of Me3-SiNPMe3 and Me3SiNP(iPr)3, respectively, with n-Butylli-thium at 20°C in n-hexane solution. They form white, moisture- and oxygen-sensitive crystals, which were characterized by IR spectroscopy and by crystal structure determinations. - [LiCH2PMe2NSiMe3]4 (1) forms a Li4 tetrahedron, the faces of which are capped with CH2 groups with average Li-C distances of 233 and 251 pm, while the nitrogen atoms occupy the corners of the Li4 tetrahedron. - [LiCMe2P(iPr)2N-SiMe3]2 (2) forms molecules of symmetry C2 in which the lithium atoms have coordination number three by two carbon atoms and one nitrogen atom with Li-C distances of 215.2 and 237.9 pm and Li-N of 192.8 pm.
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    Synthesis and Characterization of a Novel Cyclobutadiene-octatetrayne Polymer (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 269-273 
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    ISSN: 0009-2940
    Keywords: Organometallic polymers ; Coupling reactions ; Butadiynyl complexes ; Cobalt compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of 3a starting from compound 1 is described. Copper-catalyzed oxidative coupling of 3b under Hay conditions gives the novel polymer 9 with octatetrayne-cyclobutadiene units.
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    A Study on Electronic Interaction Between two [2.2]Metacyclophane Systems Connected with a C=C Bond: Preparation, Structure and Complexation of (E)- and (Z)-8,8′-(Ethene-1,2-diyl)bis(5-tert-butyl[2.2]metacyclophane) (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 289-296 
    Details
    ISSN: 0009-2940
    Keywords: Bis[2.2]metacyclophanes ; Stilbenes ; π-π Interaction ; Tricarbonylchromium complexes ; Charge-transfer ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (E)-8,8′-(Ethene-1,2-diyl)bis(5-tert-butyl[2.2]metacyclo-phane) (2) was obtained from a McMurry reaction of 5-tert-butyl-8-formyl[2.2]metacyclophane (1). Irradiation of 2 with a high-pressure mercury lamp gave the corresponding (Z) isomer 3. X-ray crystallographic analyses of 2 and 3 show a certain degree of twisting of the bond connecting the meta-cyclophane unit and the central π system due to steric crowding. UV spectra of 2 and 3 and of the charge-transfer complexes [2/TCNE] and [3/TCNE] allow for a discussion of π-π interaction between the central stilbene subunit and the outer benzene rings of the metacyclophane units. Bis[2.2]meta-cyclophanes 2 and 3 reacted regioselectively with hexacar-bonylchromium on the outer benzene rings giving 1:1 and 1:2 complexes 9-14 with tricarbonylchromium. No 1:3 and 1:4 complexes formed due to steric restrictions. Analysis of UV spectral data of the complexed [2.2]metacyclophanes was performed for an indication of π-π interactions in the complexes.
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    URL: http://dx.doi.org/10.1002/cber.19961290308
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    Thermally Stable Self-assembling Open-Frameworks: Isostructural Cs+ and (CH3)4N+ Iron Germanium Sulfides (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 283-287 
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    ISSN: 0009-2940
    Keywords: Self-assembling frameworks ; Thermal stability ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Here we report on investigations that have revealed for the first time that the Cs+ ion templates the same metal germanium sulfide open-framework as (CH3)4N+ (TMA+), and that metal complexing agents enhance crystal size by at least two orders of magnitude. The synthesis, structures and thermal properties of Cs2FeGe4S10 ·× H2O and TMA2FeGe4S10 are also described. Both have 3D zinc blende-type open-framework structures. These materials have the same connectivity as TMA2MnGe4S10. The tetrahedral sites in the lattice are alternately substituted by pseudo-tetrahedral Fe2+ and adamantanoid Ge4S104- building blocks, covalently linked together by Fe(μ-S)Ge bridge bonds, to give a tetragonal unit cell. The charge-balance of the anionic framework [Fe-Ge4S10]2- is maintained by either Cs+ or TMA+ ions in the cavity spaces. Synthesis of these materials demonstrates an interesting example of a self-assembly process in which a 3D framework is built from molecular precursors. Water adsorption-desorption cycling from room temperature to 200 °C reveals framework flexibility between larger and smaller tetragonal unit cell 14 isotypes. The compound TMA2FeGe4S10 is stable in nitrogen at 350 °C and under vacuum at 450 °C. The corresponding temperatures for Cs2FeGe4S10 are 530 °C and 630°C; it is stable on cooling to room temperature under vacuum, and after subsequent exposure to air. Six hundred thirty degrees celsius is the highest recorded temperature at which the integrity of a non-oxide framework has been maintained. The framework stability and flexibility of “all-inorganic” Cs2FeGe4S10 provides an encouraging example for researchers interested in developing sulfide-based framework materials with practical applications.
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    Complexes with S-Donor Ligands, 4Part 3: J. Vicente, M. T. Chicote, P. González-Herrero, P. G. Jones, J. Chem. Soc., Chem. Commun. 1995, 745.. Mono- and Di-Homo- and -Hetero-Nuclear Gold(I), Silver(I), and Palladium(II) Complexes with 2-(Methylthio)pyridine, Pyridine-2(1H)-thione, and Benzoxazole-2(3H)-thione. Some Examples of the Use of Complexes as Ligands (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 327-330 
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    ISSN: 0009-2940
    Keywords: Gold complexes ; Silver complexes ; Palladium complexes ; S-Donor ; Thiones ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: AgClO4 reacts with bidentate ligands 2-(methylthio)pyridine (SMepy) or complexes PPN[Au(Spy)2] [PPN = N(PPh3)2, HSpy = pyridine-2(1H)-thione) or PPN[Au(Sbz)2] (HSbz = benzoxazole-2(3H)-thione), themselves acting as ligands, to give dinuclear complexes [Ag2(μ-SMepy)2](ClO4)2 (1), [AgAu(μ-Spy)2] (2), or [AgAu(μ-Sbz)2] (3), respectively. By treating 1 with [AuCl(tht)] (tht = tetrahydrothiophene), [Au(SMepy)(tht)]ClO4 (4) is obtained which, in turn, reacts with SMepy to give [Au(SMepy)2]ClO4 (5). Similarly, [PdCl2(NCPh)2] reacts with SMepy in 1:1 molar ratio to give [Pd2Cl2(μ-Cl)2(SMepy)2] (6) which reacts with SMepy in 1:2 molar ratio to give [PdCl2(SMepy)2] (7). On the other hand, HSpy reacts with Ag2CO3 to give [Ag2(μ-Spy)2] (8), and (SMepyH)ClO4 reacts with [Au(acac)PPh3] (acacH = acetyl-acetone) to give [Au(SMepy)PPh3]ClO4 (9).
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    Zinc Complexes of Amino Acids and Peptides, 6. Zinc Complexes of Oligopeptides Containing Histidine at Both Termini (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 347-353 
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    ISSN: 0009-2940
    Keywords: Histidine peptides ; Zinc complexes ; EXAFS analysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: One tripeptide, five tetrapeptides, and one pentapeptide, all containing His-Xn-His sequences and being blocked at the N and C termini with acyl and amide functions, respectively, were synthesized by solid-phase methods. With one exception their reaction with various zinc salts led to the precipitation of 1:1 (zinc/peptide) complexes. Analytically pure compounds were obtained from zinc tetrafluoroborate and His-Gly-His (1), from zinc chloride (resp. bromide) and His-Gly -Gly-His (2), His-Ala-Gly-His (3), His-Leu-Gly-His (4), His-Pro-Gly-His (5), and His-Pro-Asn-His (6) as well as from zinc sulfate and His-Leu-Gly-His (4) and His-Ala-Pro-Gly-His (7). 1H-NMR data, when available, indicate the coordination of both histidine units to zinc in all cases. The low solubility of the complexes points to their polymeric nature. The only 1:2 (zinc/peptide) complex in this series was obtained from zinc perchlorate and His-Gly-Gly-His (2). An EXAFS study revealed that it contains zinc symmetrically coordinated by four histidine imidazole ligands. Based on the available information it is proposed that all complexes are one-dimensional polymers containg [-Zn-His-Xn-His-Zn-]x backbones.
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    Masthead (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/cber.19961290401
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    Silanediols Derived from Silanetriols. X-ray Crystal Structures of (2,4,6-Me3C6H2)N(SiMe3)Si(OSiMe3)(OH)2 and (2,4,6-Me3C6H2)N(SiMe3)Si(OSiMe2R)(OH)2 [R = CH2 (2-NH2-3,5-Me2C6H2)] (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 391-395 
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    ISSN: 0009-2940
    Keywords: Silanediols ; Silanetriols ; Siloxanes ; Hydrogen bonding ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The silanediols RN(SiMe3)Si(OSiMe3)(OH)2 (R = 2,4,6-Me3C6H2 4, 2,6-Me2C6H3 5, and 2,6-iPr2C6H3 6) were prepared by the reactions of the respective silanetriols RN(SiMe3)-Si(OH)3 1 - 3 with SiMe3Cl in THF/hexane. Silanetriol 1 in CH2Cl2/hexane solution converts over a period of 4 weeks into the silanediol (2,4,6-Me3C6H2)N(SiMe3)Si(OSiMe2 R)-(OH)2 [R = CH2(2-NH2-3,5-Me2C6H2)] (7). Compounds 4 - 7 were characterized by means of mass, IR and NMR (1H and 29Si) spectroscopy. Additionally, the molecular structures of 4 and 7 were determined by single-crystal X-ray diffraction studies. Compound 4 forms O — H…O hydrogen-bonded tetramers in the solid state. A nine-membered ring formed by an intermolecular O—H…N hydrogen bond is found in the solid-state structure of 7.
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    Novel trialkylstibane iridium(I) and iridium(III) complexes including the x-ray crystal structure of five-Coordinate [IrCl(C2H4)2(SbiPr3)2]Dedicated to Professor Erwin Weiss on the occasion of his 70th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 411-417 
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    ISSN: 0009-2940
    Keywords: Iridium complexes ; Stibane complexes ; Hydrido complexes ; Ethene complexes ; Ligand displacement reactions ; Alkyne-to-vinylidene rearrangement ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of [IrCl(C8H14)2]2 (2) with SbiPr3 in the presence of H2 yields the dihydridoiridium(III) complex cis,mer-[IrH2Cl(SbiPr3)3] (3) which on treatment with CO and with HC≡CR (R = Ph, CO2Me) affords the octahedral derivatives [IrH2Cl(CO)(SbiPr3)2] (4) and [IrHCl(C≡CR)(SbiPr3)3] (5, 6), respectively. The stibane ligand trans to hydride in 5 and 6 is rather labile and, therefore, 5 and 6 react with pyridine to give [IrHCl(C≡CR)(py)(SbiPr3)2] (7, 8). Five-coordinate bis-(stibane)iridium(I) complexes [IrCl(C2H4)2(SbR3)2] (10-12) were prepared from [IrCl(C2H4)2]2 (9) and four equiv. of SbR3 (R = iPr, Me, Ph). The X-ray crystal structural analysis of 10 reveals a distorted trigonal-bipyramidal geometry around the metal center with one stibane ligand and the two olefinic ligands in the equatorial plane. Compound 10 reacts with NaC5H5 to yield [C5H5Ir(C2H4)(SbiPr3)] (13) and with different alkynes by partial or complete displacement of the ethene ligands to give trans-[IrCl(PhC≡CPh)(SbiPr3)2] (14), [IrHCl(C≡CTol)(C2H4)(SbiPr3)2] (15), and trans-[IrCl-{=C=C(SiMe3)R}(SbiPr3)2] (16, 17), respectively.
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    Azolylborane adducts. Structural and conformational analysis by x-ray diffraction and NMR. Protic-hydric (C=Hδ+-δ-H=B) and Protic-Fluoride (C=Hδ+-δ-F=B) interactions (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 441-449 
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    ISSN: 0009-2940
    Keywords: Azolylborane adducts ; Boron-imidazole adducts ; Boron-pyridine adducts ; Protic-hydric interactions ; Protic-fluoride interactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation, NMR and X-ray diffraction studies of a series of azolylboron hydrides derived from pyrrole, indole, and carbazole coordinated with tetrahydrofuran, pyridine, and imidazole are reported. The azolyl substituents are very electroattractive leading to an acidic boron atom which strongly coordinates with the Lewis bases. The stabilization of the =BH2=groups against disproportionation could be explained in terms of the interactions found between the acidic hydrogen atoms of the heterocycles (C=Hδ+ acceptor) and the hydrides (B=Hδ- donors).
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    Masthead (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/cber.19961290501
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    The Synthesis of Stabilized Dimetallated Thioimidate Complexes by the Insertion of Ethoxycarbonylisothiocyanate into a Rhenium-Rhenium Bond (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 485-487 
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    ISSN: 0009-2940
    Keywords: Dimetallations ; Insertions ; Rhenium ; Isothiocyanates ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecules containing dimetallated hydrocarbyl groupings are of great chemical interest[1-3]. These groupings often represent intermediates in important catalytic processes[4]. Recently, we have shown that substituted dimetallated olefins can be formed by alkyne insertion into the metal-metal bonds of certain dinuclear complexes[2,5]. Complexes having dimetallated hydrocarbyl groups combined with heteroatoms are quite rare[6]. Herein is described the formation of a dimetallathioimidate grouping by the insertion of an organic isothiocyanates into an unsupported metal-metal bond. Organic isothiocyanates are useful reagents in organic synthesis[7], but the organometallic chemistry of these molecules is not yet well developed[8].
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    Supermolecules Containing a Tetrahedral Core: A New Class of Liquid-Crystalline Siloxanes (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 521-525 
    Details
    ISSN: 0009-2940
    Keywords: Liquid crystals ; Siloxanes ; Phase behaviors ; Defined topology ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that supermolecules with a tetrahedral symmetry and appropriate side-chains exhibit liquid-crystalline phase behaviour. The use of an optimised hydrosylation reaction allows for the synthesis of materials that have four mesogenic groups attached to a siloxane core, where the conformation and the configuration are unambiguous. The materials show low glass transition temperatures and, depending on the spacer length, complex liquid-crystalline morphologies.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19961290508
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    Transition Metal Complexes with Sulfur Ligands, Part 119Part 118: D. Sellmann, H.-J. Kremitzl, F. Knoch, M. Moll, J. Biol. Anorg. Chem., in press.. Synthesis of Water Soluble Fe and Ru Complexes with Novel Multidentate Thioether Thiolate Ligands Containing Carboxylate Substituents (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 509-519 
    Details
    ISSN: 0009-2940
    Keywords: Iron and ruthenium complexes ; Water soluble complexes ; Sulfur ligands ; X-ray structure analyses ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In search of water soluble transition metal complexes with sulfur dominated coordination spheres that model key reactions of nitrogenases, the benzenedithiol derivatives ‘CO2HS2’-H2 (1) and ‘CO2Me-S2’-H2 (2) were synthesized as precursors for multidentate sulfur ligands. The template alkylation of 2 by C2H4Br2 at [Fe(CO)2] fragments yielded a mixture of two diastereomeric C2 symmetrical [Fe(CO)2(‘CO2Me-S4’)] complexes (4a and 4b), which were separated by crystallization. The hydrolysis of the mixture of the diastereomers 4a and 4b led to the isomerically pure tetradentate thioether thiol ligand ‘CO2Me-S4’-H2 (5) proving the regioselectivity of the template alkylation of the asymmetrical dithiol 2. The C1 symmetrical [Fe(‘CO2Me-S2’)2]2- anion is an intermediate of the template alkylation and was isolated as (AsPh4)2 [Fe(‘CO2Me-S2’2] (11), 4a, 5 and 11 were characterized by X-ray structural analysis. Saponification of the methyl ester groups of 5 yielded ‘CO2H-S4’-H2 (7). Treatment of 7 with FeCl2 · 4 H2O in the presence of CO and LiOMe gave a mixture of two C2 symmetrical and water soluble diastereomers of Li2[Fe(CO)2(‘CO2-S4’)] (8). Upon treatment with [RuCl2 (PPh3)3] 7 yielded isomerically pure [Ru(PPh3)2-(‘CO2H-S4’)] (9). 9 also exhibits C2 symmetry and could be reversibly deprotonated to form the water soluble complex K2[Ru(PPh3)2 (‘CO2-S4’)] (10). Treatment of (NBu4)2 (‘CO2MeS2’) with “Ru(NO)Cl3” led to isomerically pure (NBu4)[Ru(NO)(‘CO2Me-S2’)2] (12).
    Additional Material: 6 Ill.
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    Syntheses and Photochemistry of Fluorinated and Chlorinated Titanium Porphyrinates: Crystal Structure of Oxotitanium meso-Tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrinate (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 833-836 
    Details
    ISSN: 0009-2940
    Keywords: Oxotitanium(IV) porphyrinate ; Peroxotitanium(IV) porphyrinate ; Photochemistry ; Singlet oxygen ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The syntheses of oxotitanium(IV) meso-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrinate O=Ti(TPPF20) (1), oxotitanium(IV) meso-tetrakis(2,6-difluorophenyl)porphyrinate O=Ti-(TPPF8) (3), and oxotitanium(IV) meso-tetrakis(2,6-dichlorophenyl)porphyrinate O=Ti(TPPCl8) (5) from titanium tetrachloride and the corresponding porphine are described. The structure of 1 was determined by single-crystal X-ray diffraction. The reaction of oxotitanium porphyrinates with aqueous hydrogen peroxide leads to the corresponding light-sensitive peroxotitanium(IV) complexes: Ti(O2)(TPPF20) (2), Ti(O2)-(TPPF8) (4), Ti(O2)(TPPCl8) (6). All complexes are efficient and stable photosensitizers for the generation of singlet oxygen.
    Additional Material: 2 Ill.
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    Syntheses of Hetero-sila-closo-boranes (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 837-839 
    Details
    ISSN: 0009-2940
    Keywords: Boron compounds ; Silaboranes ; Dihetero-closo-borane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Addition of 3 equivalents of KH · BEt3 to [Me3NH][Me-SiB10H12] followed by addition of one equivalent of SnCl2 or SbI3 affords the stanna-sila-closo-borate(1-) 3 and stiba-sila-closo-borane 4, respectively. [MePh3P] · 3 crystallizes in the orthorhombic space group P212121.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19961290716
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    Intramolekular stabilisierte Übergangsmetallamide: 2-(Dimethylaminomethyl)pyrrolyl-Komplexe des Titan(III), Vanadium(III), Chrom(III), Cobalt(II) und Nickel(II) (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 853-857 
    Details
    ISSN: 0009-2940
    Keywords: Amides ; Pyrrolyl complexes ; Chelate complexes ; Transition-metal complexes ; Metallacycles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Intramolecularly Stabilized Metal Amides: 2-(Dimethylaminomethyl)pyrrolyl Complexes of Titanium(III), Vanadium(III), Chromium(III), Cobalt(II) and Nickel(II)By the metallation of 2-(dimethylaminomethyl)pyrrol (HL) with butyllithium the lithium pyrrolide LiL (1) was obtained. The reactions of 1 with TiBr3 · 3 THF, VBr3 · 3 THF, CrBr3 · 3 THF, CoBr2 · 2 THF, and NiBr2 · 1.67 THF result in the formation of the 2-(dimethylaminomethyl)pyrrolyl complexes of type ML3 (2-4), and ML2 (5, 6), respectively. The structures of these new compounds are discussed on the basis of magnetic and visible absorption measurements. An X-ray crystal structure determination of 4 reveals a strongly distorted octahedral environment of the chromium atom with facial arrangement of the ligands.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19961290719
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    Stepwise Insertion of Alkylisocyanides into the Metal-Alkyne Bond of Half-Sandwich Type Rhodium Complexes: Synthesis and Structural Characterization of Metallacyclobutenes and MetallacyclopentenesDedicated to Professor Gerhard E. Herberich on the occasion of his 60th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 903-910 
    Details
    ISSN: 0009-2940
    Keywords: Rhodium complexes ; Alkyne complexes ; Insertion reactions ; Alkyl isocyanides ; Metallacycles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cyclopentadienyl complexes [C5H5Rh(RC≡CR′)(SbiPr3)] (5-8), which were prepared from trans-[RhCl-(RC≡CR′)(SbiPr3)2] (1-4) and NaC5H5 and which contain a labile Rh-SbiPr3 bond, reacted with CO and CNR″ (R″ = Me, tBu) to give the carbonyl and isocyanide derivatives [C5H5Rh(RC≡CR′)(CO)] (9-11) and [C5H5Rh(RC≡CR′)-(CNR″)] (12-16), respectively. On treatment of 12 (R = R′ = Ph; R″ = Me) with SbiPr3, the metallacyclobutene complex [C5H5Rh{κ2(C,C}-C( = NMe)CPh=CPh}(SbiPr3)] (17) was formed; it reacts with excess CNMe or CNtBu to yield the metallacyclopentenes [C5H5Rh{κ2(C,C)-C(=NMe)CPh=CPhC-(=NR)}(CNR)] (18, 19). Similar compounds 20-23 containing a five-membered RhC4 metallacycle were prepared either from [C5H5Rh(RC≡CR′)(SbiPr3)] (7, 8) or [C5H5Rh-(PhC≡CPh)(CNtBu)] (14) and excess isocyanide. The crystal and molecular structures of 17 and 18 (R = Me) have been determined.
    Additional Material: 3 Ill.
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    Isolation and Spectroscopic Characterization of Heteroleptic, Anionic and Neutral (Phthalocyaninato)(tetra-4-pyridylporphyrinato)lanthanide(III) Double-DeckersDedicated to Professor Shang-Wai Tam on the occasion of his retirement from The Chinese University of Hong Kong. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 933-936 
    Details
    ISSN: 0009-2940
    Keywords: Phthalocyanines ; Porphyrins ; Lanthanide(III) compounds ; Macrocyclic ligands ; Double-decker complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of 5,10,15,20-tetra-4-pyridylporphyrin [(TPyP)H2] with europium(III) or gadolinium(III) acetylacetonate [Ln(acac)3 · nH2O] (Ln = Eu, Gd) in 1,2,4-trichlorobenzene produced Ln(acac)(TPyP), which reacted with dilithium phthalocyaninate [Li2(Pc)] to give Li[Ln(Pc)(TPyP)] in moderate yields. Upon exposure to air, solutions of these compounds converted slowly to the corresponding neutral complexes Ln(Pc)(TPyP). The new compounds were spectroscopically characterized.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19961290809
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    Synthesis, Spectroscopic Characterization, and Crystal Structure Determination of Cationic [(Cyclopentadienyl)dicarbonyliron](alkynyl)-aminocarbene Complexes (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 937-944 
    Details
    ISSN: 0009-2940
    Keywords: Iron acyl complexes ; (Alkynyl)carbene ligand ; Cationic aminocarbene complexes ; Iron (2-methoxyvinyl)aminocarbene complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: (Alkynoyl)iron complexes 1, Cp(CO)2Fe(O=CC≡CR) (R = CH3, Ph, SiMe3), were synthesized by applying a mixed anhydride procedure and transformed into the cationic methoxycarbene complexes 2, [Cp(CO)2 Fe(C(OMe)C≡CR)+]-[PF6-]. Primary amines H2NR′ react with the methoxycarbene complexes to furnish exclusively cationic aminocarbene complexes 3, [Cp(CO)2 Fe(C(NHR′)C≡CR)+][PF6-], or (2-methoxyvinyl)aminocarbene complexes 5. The spectroscopic properties of the new complexes are discussed. The (alkynyl)-aminocarbene complexes 3e and 3f were characterized by X-ray crystal structure analysis.
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    URL: http://dx.doi.org/10.1002/cber.19961290810
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    Synthesis and Characterization of Novel Phthalocyanines with Four 16-Membered Diazadithia Macrocycles (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 967-971 
    Details
    ISSN: 0009-2940
    Keywords: Phthalocyanines, sulphonated ; Diazadithiamacrocycles ; Pentanuclear complex ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metal phthalocyanines (M = Cu, Ni, Co) 3-5 bearing four 16-membered diazadithia macrocycles at the peripheral positions were prepared. Detosylation with concentrated sulfuric acid afforded products containing both sulfonated groups on the aromatic rings of the macrocyclic substituents which are excellently soluble in water and donor sites for binding four CuII ions to give a pentanuclear complex.
    Additional Material: 2 Tab.
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    A Search for Thionitrosyl Chloride (Cl-N=S) in the Gas Phase (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1379-1381 
    Details
    ISSN: 0009-2940
    Keywords: Thionitrosyl chloride ; Thiazyl chloride ; Neutralization-reionization mass spectrometry ; Calculations, ab initio ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ab initio MO calculations at the QCISD(T)/6-311++G(3df,2p) + ZPE level show that the thionitrosyl chloride ion, ClNS+•, is 36 kJ/mol more stable than the thiazyl chloride ion, NSCl+•, whereas neutral NSCl is 77 kJ/mol more stable than ClNS [IEa (ClNS) = 9.2 ± 0.3 eV, IEa (NSCl) = 10.5 ± 0.3 eV]. Mild flash-vacuum pyrolysis of the thiazyl chloride trimer (NSCl)3 followed by electron impact ionization resulted in the formation of [N,S,Cl]+• ions (m/z 81). The fragments observed in the CA spectrum of these ions indicate the formation of both NSCl+• and ClNS+• ions. A very weak recovery signal is observed in a neutralizationreionization experiment. This signal is tentatively assigned to the neutral thionitrosyl chloride.
    Additional Material: 4 Ill.
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    Synthesis and Reactivity of Some Nitroaryl Complexes of HgII and AuIII  -  Synthesis of a Substituted Biphenyl by C-C Coupling - Crystal Structure of [Hg(C6H4NO2-3, OnBu-6)2] (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1395-1399 
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    ISSN: 0009-2940
    Keywords: Gold ; Mercury ; Nitroaryl ; Transmetallation ; Biaryl ; C-C Coupling ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-Butoxynitrobenzene reacts with [Hg(O2CCF3)2] and LiCl to give [Hg(R)Cl] [R = C6H3NO2-3, OnBu-6 (1)] which is symmetrized by Me4NCl to give [HgR2] (2), the crystal structure of which has been determined. The reaction of 2 with Me4N[AuCl4] affords Me4N[Au(R)Cl3] (3) by a facile transmetallation process. Complex 3 reacts with PPh3 (1:1) to give cis-[Au(R)(PPh3)Cl2] (4). The diaryl complex [-Ph-2)(R)Cl] (5) is obtained by reaction of 3 with [Hg-(C6H4N=NPh-2)2] through a second transmetallation reaction. Complex 5 and PPh3 (1:1) give [AuClPPh3] and the C-C coupling biphenyl RC6H4N=NPh-2 (6).
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    URL: http://dx.doi.org/10.1002/cber.19961291114
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    Sulfenato, Thiosulfinato, and Thiosulfonato Transition Metal ComplexesDedicated to Professor M. Herberhold on the occasion of his 60th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1409-1419 
    Details
    ISSN: 0009-2940
    Keywords: Sulfenic acid anions ; Thiosulfinic acid anions ; Thiosulfonic acid anions ; Transition metal complexes ; Stereochemistry ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and coordination chemistry of sulfenic, thiosulfinic, and thiosulfonic acid anions are reviewed. Different approaches, which yield the platinum(II) and ruthenium(II) complexes containing the anionic sulfur(0), sulfur(II), and sulfur(IV) oxid ligands, are described. The oxidative addition of thiosulfinates or N-sulfinyl phthalimides to platinum(0) complexes L2Pt(C2H4) [L = PPh3, 1/2 PPh2CH2CH2PPh2, 1/2 (R,R)-(-)-DIOP, 1/2 (C5H4PPh2)Fe(C5H4PPh2) leads to sulfenato complexes; those of N-thiosulfinyl phthalimidies or trisulfid 1-oxides afford the thiosulfinato complexes. Moreover, the reactions of CpRu(PPh3)(L)(SH) (L = CO, PPh3) with N-sulfinyl phthalimides forming the thiosulfinato moiety, are reported. The spectroscopic, structural and chemical properties of these complexes are discussed.
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    Cationic Iron Aminocarbene Complexes as Dienophiles in Diels-Alder Reaction with Cyclopentadiene (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1057-1059 
    Details
    ISSN: 0009-2940
    Keywords: (Alkynyl)carbene ligands ; Iron acyl complexes ; Cationic iron aminocarbene complexes ; Diels-Alder reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cationic iron (alkynyl)aminocarbene complexes [Cp(CO)2Fe(C(NHR)C≡CSiMe3][PF6], (R = C6H5, p-CH3C6H4) 1 derived from aromatic amines smoothly react with cyclopentadiene in dichloromethane to yield the cycloadducts 2. No reaction was observed for complexes derived from sterically demanding aliphatic amines, like L-alanine tert-butyl ester. For comparison, the alkynyl-substituted acyl iron compounds Cp(CO)2Fe(C=O)C≡C̊ (R = SiMe3, C6H5) 3 were investigated, requiring TiCl4 catalysis to undergo the cycloaddition reaction. The structures of the cycloadducts 4 were determined by X-ray crystallography.
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    URL: http://dx.doi.org/10.1002/cber.19961290913
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    Synthesis, Structure and Reactions of the Homoleptic Alkyne Nickel(0) Complex (Alkyne)4Ni3 (Alkyne: 2-methyl-4-trimethylsilyl-3-butyn-2-ol)Dedicated to Professor Walter Siebert on the occasion of his 60th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1457-1461 
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    ISSN: 0009-2940
    Keywords: Nickel(0) ; Alkyne complexes ; Hydrogen bonds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of (cdt)Ni (cdt: cyclododeca-1,5,9-triene) with 2 equivalents of 2-methyl-4-trimethylsilyl-3-butyn-2-ol leads to the selective formation of the homoleptic complex (alkyne)4Ni3 (compound 3), which can be isolated in excellent yields. The solid-state structure of 3 exhibits three Ni centers, forming a bent Ni3 chain connected by two bridging alkynes. The other two alkynes are terminally coordinated. Additionally, the trimeric units are stabilized by three intramolecular hydrogen bonds. Two intermolecular hydrogen bonds connect the trimeric units to form a polymer rope. According to the 13C- and 1H-NMR spectra in THF the structure of the complex 3 in solution is very similar to that in the solid state. The reaction of 3 with some alkynediols and with 2,5,5-trimethylhex-3-yn-2-ol affords compounds of the type (alkyne)2Ni. Cot (cot: 1,3,5,7-cyclooctatetraene) converts 3 into [(cot)Ni]2, which in turn reacts with 2,5-dimethylhex-3-yne-2,5-diol to form the dimeric complex (alkyne)2Ni2(cot) 6. X-ray analysis of 6 reveals a very symmetrical structure in which cot connects both Ni(0) centers at opposite sides of the ring system.
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    Control of the SO2 Coordination Mode at the (Monochelate)rhodium Complex ClRh(P∼O) with the Hemilabile Ligand Cy2PCH2CH2OCH3Dedicated to Professor Michael Hanack on the occasion of his 65th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1103-1105 
    Details
    ISSN: 0009-2940
    Keywords: Sulfur dioxide ; Rhodium complexes ; Ether-phosphanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The SO2 coordination mode at the rhodium complex [ClRh(P∼O)()] (1) [ = η2(O,P)-chelated Cy2PCH2CH2OCH3 ligand; P∼O = =1(P)-coordinated] is controlled by the hemilabile ligand Cy2PCH2CH2OCH3 and shows a dependence on the polarity of the solvent. In polar organic solvents (e.g. acetone) the addition of sulfur dioxide results in the formation of a trigonal-pyramidal oriented SO2 group in [ClRh(η1-SO2)(P∼O)()] (2a). However, in nonpolar media (e.g. n-hexane) a trigonal-coplanar geometry of the SO2 unit in [ClRh(η1-SO2)(P∼O)2] (2b) is favored.
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    Masthead (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961291001
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    1,3-Heterobinuclear Cyclobutenylidene Complexes with an Exocyclic C=C bond  -  Synthesis, Structure, and Spectroscopic Properties (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1475-1482 
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    ISSN: 0009-2940
    Keywords: Allenylidene complexes ; Alkynyl complexes ; Cyclobutenylidene complexes ; Cycloadditions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pentacarbonyl(allenylidene)chromium and -tungsten, [(CO)5—M=C=C=CR2] (M=Cr, R=C6H4CH3-p(1a), C6H4OCH3 (1b); M=W, R=C6H4CH3-p (1c), react with the alkynyl complexes [Cp(CO)2Fe—C≡CR′] (R′ = nBu (2), Ph (4)), [Cp*(CO)2Fe—C≡CnBu] (6), [Cp(CO){P(OMe)3}-Fe—C≡CnBu] (8) and [Cp(PPh3)Ni—C≡CnBu] (10) by cycloaddition of the C≡C bond of the alkynyl complexes to the Cα=Cβ bond of the allenylidene ligand to give 3a-c), (5), (7), and respectively. The cycloaddition is highly selective. The spectroscopic data of these 1,3-heterobinuclear complexes indicate a delocalized π-system (M=Cr, W; Y=[Fe(CO)2Cp], [Fe(CO)(P{OMe}3)Cp], [Fe(CO)2Cp*], [Ni(PPh3)-Cp]). X-ray structural analyses of the compounds 3a, 9a, and 11c reveal a “butterfly” conformation of the four-membered ring. Its puckering angle is 142° (3a), 152° (9a), and 151° (11c). All Complexes exhibit a moderate to strong negative solvatochromic behavior. The extent of the solvatochromic effect depends on [(CO)5M] and Y and considerably decreases when C=CR2 is replaced by e.g. CMe2.
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    The Phosphonate-Phosphate- and Phosphate-Phosphonate Rearrangement and Their Applications, 4Part 3: Ref.[1].. Deprotonation of Secondary Benzylic Phosphates  -  Configurationally Stabile Benzylic Carbanions with a Diethoxyphosphoryloxy Substituent and Their Rearrangement to Optically Active Tertiary α-Hydroxyphosphonates (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1503-1508 
    Details
    ISSN: 0009-2940
    Keywords: Phosphate - Phosphonate rearrangement ; Carbanions, benzylic, configurational stability of ; α-Hydroxyphosphonates, tertiary, chiral, non-racemic ; t-Butyl(phenyl)phosphinothioic acid, homochiral ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optically active alcohols (ee ≥ 98%) such as 1-phenylpropanol, 1-(2-naphthyl)ethanol, 1-tetralol, and 1-indanol were transformed into diethyl phosphates 7a-d. sBuLi/TMEDA  -  induced phosphate - phosphonate rearrangement in diethyl ether furnished tertiary α-hydroxyphosphonates 8a-d of high enantiomeric purity (ee 94-98%) in yields of 43-83% with retention of configuration. The enantiomeric excesses were determined by using homochiral t-butyl(phenyl)phosphinothioic acid as chiral solvating agent.
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    Hydride Addition to Coordinated S2CPR3 Ligands in Mononuclear Mn and Re Complexes: Phosphane-dithioformate Adducts as Five-electron Bridging Ligands (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1535-1540 
    Details
    ISSN: 0009-2940
    Keywords: 1,1-Dithiolate ; Manganese complexes ; Rhenium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cationic tetracarbonyl complex cis-[Mn(CO)4-(S2CPCy3)]+ undergoes addition of hydride ion to the central carbon of the S2CPR3 ligand to afford, after spontaneous dimerization with loss of CO, the dimer [Mn2(CO)6{μ-S2C(H)PCy3}2] (5a), which was characterized by analytical and spectroscopic methods as well as by X-ray diffraction. In the molecule of 5a each S2C(H)PCy3- ligand is coordinated to one manganese in an η2-S,S′ chelate fashion, and one sulfur of each ligand serves as a bridge to bind the other manganese atom, thus forming a distorted Mn2S2 square. This appears to be a very stable arrangement. Compound 5a can be more easily prepared by treating the perchlorato complex [Mn(CO)3(S2CPCy3)(OClO3)] (2a) with NaBH4. This procedure is general and can be used for the preparation of several derivatives containing either manganese or rhenium [M2(CO)6{μ-S2C(H)PR3}2] 5a-d. The reaction of cationic tricarbonyl complexes [M(CO)3(S2CPR3)(PPh3)]PF6 (M = Mn, Re) with NaBH4 produced the same dimers 5a or 5c by displacement of the PPh3 ligand. Treatment of the dimer 5a with excess PEt3 or P(OMe)3 leads to the cleavage of the bridges and loss of one CO and the PR3 group from the S2C(H)PR3 unit to afford ultimately the dithioformate complexes [Mn(CO)2(S2CH)(L)2] [L = PEt3, P(OMe)3].
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19961291221
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    Zinkorganische Phosphaniminato-Komplexe mit Heterocuban-StrukturHerrn Prof. Dr. Armin Berndt zum 60. Geburtstag gewidmet. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1621-1625 
    Details
    ISSN: 0009-2940
    Keywords: Organo-zinc compounds ; Phosphaneiminato complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organo-Zinc Phosphaneiminato Complexes with Heterocubane StructureThe organo-zinc heterocubanes [ZnR(NPMe3)]4 with R = CH3 (1) and n-C4H9 (2) were prepared by the reaction of [ZnBr(NPMe3)]4 with MeLi and nBuLi, respectively, in hexane solution. In a similar reaction of nBuLi with [ZnI(NPMe3]4 the phosphaneiminato complex [Zn4I(nBu)4(NPMe3)3] (3) is formed. 1-3 were characterized by IR, NMR and MS spectroscopy, and by crystal-structure determinations. 1 and 2 possess heterocubane structures in which the zinc atoms are linked via μ3-N bridges of the phosphaneiminato groups, and all bond angles in the Zn4N4 core are close to 90°. A distorted heterocubane structure is observed for 3 with one of the NPMe3 moieties replaced by an iodine atom.
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    On the Synthesis of Sulfoxonium Ylides: New Aspects of the Chemistry of 1,3-Dithietane 1,1,3,3-Tetraoxide and 1,3,5-Trithiane 1,1,3,3,5,5-Hexaoxide (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 161-167 
    Details
    ISSN: 0009-2940
    Keywords: Sulfoxonium ylides ; 1,3-Dithietane 1,1,3,3-tetraoxide, silylated ; 1,3,5-Trithiane 1,1,3,3,5,5-hexaoxide, silylated ; Disulfenes, unsaturated ; Disulfenes, dianions of ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sulfoxonium ylides 3a-h were synthesized by silylation of the cyclic methylene disulfones 1,3-dithietane 1,1,3,3-tetraoxide (1) and 1,3,5-trithiane 1,1,3,3,5,5-hexaoxide (4) with the silylating agents silyl nonafluorobutanesulfonates. The structure and constitution of the ylides were established with 1H-NMR, 13C-NMR, 29Si-NMR spectroscopy, mass spectrometry, and elemental analysis. On the route to the sulfoxonium ylides a new class of unsaturated disulfenes 7, 8, 12, 13 of 1 and 4 were synthesized via Knoevenagel and substitution reactions. Dianions of newly formed alkyl disulfenes 16a, b, e, f, and the trianion 17 were prepared and characterized by 1H-NMR and 13C-NMR spectroscopy and compared with the results of the ylides.
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    URL: http://dx.doi.org/10.1002/cber.19961290209
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    Addition von CS2 und anderen Heteroallenen an die 16-Elektronen-Osmium(0)-Komplexe trans-[OsCl(NO)(PiPr2R)2] (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 405-410 
    Details
    ISSN: 0009-2940
    Keywords: Osmium(0) complexes ; Nitrosyl complexes ; CS2, COS, SCNPh, and Ph2C=C=O as bidentate ligands ; Protonation and methylation reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Addition of CS2 and Other Heteroallenes to the 16-Electron Osmium(0) Complexes trans-[OsCl(NO)(PiPr2R)2]The coordinatively unsaturated 16-electron compounds trans-[OsCl(NO)(PiPr2R)2] (1: R = iPr; 2: R = Ph) react with CS2 and COS to form the 1:1 adducts [OsCl(NO){κ2(C,S)-S=C=S}(PiPr2R)2)] (3, 4) and [OsCl(NO){κ2(C,S)-S=C=O}-(PiPr2R)2] (6, 7), respectively. While compounds 3, 4 are inert toward PMe3, the Os(COS) complexes 6, 7 react with tri-methylphosphane by abstraction of sulfur to give (OsCl(NO)-(CO)(PiPr2R)2] (8, 9). From 1 or 2 and phenylisothiocyanate the corresponding 1:1 adducts (OsCl(NO){κ2(C,S)-S=C=NPh}(PiPr2R)2] (10, 11) are obtained. Protonation and methylation reactions of 10 (R = iPr) with HBF4 or CF3SO3Me lead, by addition of the electrophile to the C=N nitrogen atom, to the formation of [OsCl(NO){κ2(C,S)-S=CNHPh}-(PiPr3)2]BF4 (12) and [OsCl(NO){κ2(C,S)-S=CN(Me)Ph}-(PiPr3)2]CF3SO3 (13). Treatment of 1 with diphenylketene yields [OsCl(NO){κ2(C,O)-O=C=CPh2}(PiPr3)2] (14). The X-ray structure analyses of 10 and 14 confirm the coordination of phenylisothiocyanate via S and C and of diphenylketene via O and C, respectively.
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    8-quinolylcyclopentadienyl, a ligand with a tailored fit for chelate complexes (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 459-463 
    Details
    ISSN: 0009-2940
    Keywords: Cyclopentadienes ; Half-sandwich complexes ; Intramolecular nitrogen donors ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 8-Lithioquinoline reacts with 2,3,4,5-tetramethylcyclopentenone to give 8-quinolylcyclopentadiene (1/2) after acidic workup and treatment with ammonia. Two of the possible three isomers are formed; the acidic protons on the Cp rings show unusual downfield shifts in the 1H-NMR spectra. Treatment with strong bases led to the intensely coloured anionic 4 which was converted into the trimethylsilyl derivative 5. This is a suitable starting compound for the trihalotitanium and -zirconium compounds 6 and 7. The two complexes were investigated by crystal structure analyses. In both cases the quinolyl nitrogen atom is coordinated to the metal.
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    URL: http://dx.doi.org/10.1002/cber.19961290415
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    Über das Silaethen tBu2Si=C(SiMe3)2 und die Struktur sowie Reaktivität seines [4 + 2]-Cycloaddukts mit Ph2C=OFrau Prof. Marianne Baudler zum 75. Geburtstag gewidmet. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 471-478 
    Details
    ISSN: 0009-2940
    Keywords: Silaethenes ; [4 + 2] Cycloadditions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On the Silaethene tBu2Si=C(SiMe3)2, and the Structure and Reactivity of Its [4 + 2] Cycloadduct with Ph2C=OFrom tBu2SiF—CLi(SiMe3)2 by LiF elimination only Me2Si= C(SiMe3)(SiMetBu2) (1b) instead of tBu2Si=C(SiMe3)2 (1a) is isolated. With benzophenone, silaethene 1b (from its THF adduct 1b · THF) forms at -78 °C a yellow [4 + 2] cycloadduct (5) and a colorless [2 + 2] cycloadduct (6). With increasing temperature 5 transforms into 6, and 6 transforms -more slowly - into the yellow [4 + 2] cycloadduct (7) of 1a and Ph2CO. It follows from this that the migration equilibrium 1a ⇄ 1b really exists. The structure of 7 shows a planar —O—CPh=C6H5-framework with the cycloadded atoms Si and C from -tBu2Si—C(SiMe3)2- located above the plane. The =C6H5—C bond (1.62 Å) is exceptionally long. 7 is a source for 1a which is trapped by acetone (formation of an ene product) and by benzaldehyde [formation of a [2 + 2] cycloadduct, unstable against cycloreversion into PhHC=C(SiMe3)2 and tBu2SiO-containing substances]. Reaction of 7 with trimethylsilyl azide, less reactive than acetone or benzaldehyde, leads - by way of 1a which transforms into 1b - to a trapping product of 1b (formation of a [3 + 2] cycloadduct, unstable against transformation into (RMe2Si)(Me3Si)CN2 with R = (Me3Si)2N, or cycloreversion into (tBu2MeSi)(Me3Si)CN2 and Me2SiNSiMe3-containing substances). Reaction of 1b or 1b · THF with acetone leads only to an ene reaction product of 1b. This means, that only undetectable amounts of 1a or 1a · THF are in equilibrium with 1b or 1b · THF. A minor substance which is shown by NMR at low temperatures besides 1b or 1b · THF is interpreted as a rotamer of 1b or 1b · THF.
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    Organophosphorus Compounds, 112Part 111: Ref.[1].. Lewis Acid Mediated Spirocyclotrimerization of Kinetically Stabilized Phosphaalkynes - Key Step for the Selective Generation and Trapping of Triphospha Dewar BenzenesDedicated to Professor H. W. Roesky on the occasion of his 60th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 489-494 
    Details
    ISSN: 0009-2940
    Keywords: Phosphaalkynes ; Phosphaalkenes ; Spirocyclotrimerization ; Triphospha Dewar benzenes ; Phosphaalkyne cyclooligomers ; Cage compounds, phosphorus-carbon ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the presence of Lewis acidic derivatives of group 13 elements, phosphaalkynes 7 undergo spirocyclotrimerization with incorporation of the corresponding Lewis acids to form 10a-f. Scope and limitations of this novel cyclooligomerization process are examined. Starting from the spirocyclotrimer 10a reaction with the Lewis base dimethyl sulfoxide, we have in hand for the first time a method for the selective generation of two isomeric triphospha Dewar benzene derivatives (18, 19). Both can be trapped efficiently by further reaction with the phosphaalkyne to furnish the two novel phosphaalkyne cyclotetramers 20 and 21, both still possessing a phosphorus-carbon double bond. In the case of 21, further functionalization of the phosphaalkene unit is possible by [3 + 2] cycloaddition with a nitrile oxide (→ 23).
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    URL: http://dx.doi.org/10.1002/cber.19961290504
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    Self-Assembly of Substituted 6-Hydroxy-trans-3-hexenoic Acids - Formation of Extended Ribbon-Like Structures by Hydrogen Bonds (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1029-1034 
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    ISSN: 0009-2940
    Keywords: Hydrogen bonding ; Hydroxy carboxylic acids, self-assembly of ; Crystal engineering ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The substituted 6-hydroxy-trans-3-hexenoic acids 2a and 2b are prepared by an organometallic template reaction involving a sequence of CC coupling reactions between a CO2 equivalent, butadiene, and 3-cyclopenten-1-one or 3,4-diphenyl-3-cyclopenten-1-one, respectively. In the crystal 2a assembles to form an infinite ribbon-type structure, exhibiting an alternating array of 12 and 18 atom-containing loops. The former are each constructed by an alternating CO2H/OH/CO2H/OH sequence, originating from four different monomeric units, that are linked together by means of hydrogen bonds. Two complementary ribbons of 2a are connected by van der Waals interactions to form staples that constitute the microscopic building blocks of the true (2a)n structure in the crystal. Stacks of cyclopentene π bonds are oriented inside the columnar structure of 2a. Acid 2b also forms a related ribbon-like assembly in the solid state. Here the bulky 3,4-diphenylcyclopentadienylidene moieties are oriented laterally at the ribbons, and van-der-Waals interactions with adjacent ribbons construct a three-dimensional hydroxyhexenoic acid network.
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    Preparation and Structure of Dithioxo- and Diselenoxophosphoranes Stabilized by Intramolecular Coordination with a Dialkylamino GroupDedicated to Prof. Dr. Marianne Baudler on the occasion of her 75th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1049-1055 
    Details
    ISSN: 0009-2940
    Keywords: Dithioxophosphoranes ; Diselenoxophosphoranes ; Internal coordination ; Steric protection ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Some dithioxophosphoranes 3 stabilized by intramolecular coordination with a dialkylamino group were prepared, and their structures were analyzed by X-ray crystallography involving [2,4-di-tert-butyl-6-(isopropylmethylamino)phenyl]- (3c), {2,4-di-tert-butyl-6-[(dimethylamino)methyl]phenyl}- (3f), and {2,4-di-tert-butyl-6-[2-(dimethylamino)-1,1-dimethylethyl]phenyl}dithioxophosphorane (3h). The bond between the phosphorus atom and the aromatic ring is flexible and the angle narrows with decreasing ring size of the intramolecular coordination. The 31P-NMR signals are shifted to higher field with increasing ring size of the intramolecular coordination or strength of coordination. Similarly, the corresponding diselenoxophosphoranes 4 were prepared. Both their 31P- and 77Se-NMR signals are shifted to higher field with increasing contribution of intramolecular coordination.
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    Structural Studies on Indium and Tin Thiobenzoates (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1093-1098 
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    ISSN: 0009-2940
    Keywords: Indium tris(thiobenzoate) ; Triethylammonium tetrakis(thiobenzoato)indate ; Tin, butyl-, tris(thiobenzoate) ; Tin, dichloro-, bis(thiobenzoate) ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Indium(III) and tin(IV) thiocarboxylates were prepared and characterized on the basis of their IR, 13C- and 19Sn-NMR data. Indium tris(thiobenzoate) (1) decomposes into a sulfido complex In (S)[S(O)CPh] (2a). The corresponding tris(thioacetate) In[S(O)CMe]3 is thermally too unstable to be isolated. The anionic tetrakis complex [Et3NH]{In[S(O)CPh]4} (3) was characterized by X-ray crystallography which revealed a distorted tetrahedral coordination at the In atom. X-ray diffraction analysis of the complexes BuSn[S(O)CPh]3 (4) and Cl2Sn[S(O)CPh]2 (7) showed distorted tetrahedral and cis-octahedral structures, respectively.
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    Reaktionen des Tripod-Co-Templats CH3C(CH2PPh2)3Co(II) mit funktionalisierten HydrazinenMax Herberhold zum 60. Geburtstag gewidmet. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1107-1113 
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    ISSN: 0009-2940
    Keywords: Tripod ligands ; Hydrazines, substituted ; Diazenes ; Cobalt(III), fivefold coordination of ; Cobalt(II), fivefold coordination of ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The coordination behaviour of ligands having the same basic constitution RN=NC(=X)R′ (X = O, NR″, S) in their tripod cobalt derivatives has been analyzed. The ligands themselves may be considered as neutral heterodiene compounds and are in this respect vinylogues to diazenes RN=NRy′. Two- electron reduction of these neutral species results in dianionic heterosubstituted heteroolefins RN- -N=C(X-)R′. Due to their redox ambiguity the oxidation state of the metal M in chelate complexes is not a priori evident. Compounds tripod [5: X, R′ = O, Ph; 6; (X, R′) = (py); 7: X, R′ = S, NH2] are best described as containing low-spin Co(III) and dianionic ligands. Co(II) species are obtained with diethyl azodicarboxylate EtOOCN=NCOOEt as the ligand. In the mononuclear compound, with only one nitrogen and one carbonyl oxygen of the ligand acting as donor groups, the neutral ligand is coordinated to give the high-spin cobalt(II) species tripod (8). In the dinuclear compound 9 with both of the nitrogen atoms and carbonyl groups involved in coordination the dianionic ligand bridges two high-spin cobalt(II) centers to give tripod (9) as a derivative with two fused five-membered chelate rings. In addition to the conventional analytical techniques X-ray structure analyses, cyclovoltametric measurements, magnetic susceptibility and ESR data are used to characterize the compounds.
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    Übergangsmetall-Stannyl Komplexe, 10[1]. Molybdocen- und Wolframocen-Derivate mit zwei unterschiedlichen Liganden der 4. Hauptgruppe (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1131-1142 
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    ISSN: 0009-2940
    Keywords: Stannyl complexes ; Plumbyl complexes ; Tungsten complexes ; Molybdenum complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transition-Metal Stannyl Complexes, 10 - Molybdocen and Wolframocen Derivatives with Two Different Main-Group-4 LigandsReactions of Li[Cp2MSnPh3] (M = Mo, W) with CH3I, BuBr, PhCH2Br, PhC(O)Cl or Br(CH2)nBr (n = 4,5) yield Cp2M(R)SnPh3 [R = CH3, Bu, CH2Ph, C(O)Ph, (CH2)nBr], while tBuBr or CH3C(O)Cl give the hydrido complexes Cp2M(H)SnPh3. A silyl stannyl complex is only obtained from Li[Cp2WSnPh3] and Me3SiOSO2CF3, but not with Me3SiCl or from the anionic Mo complex. In contrast, the reactions of chlorostannanes provide the bis(stannyl) complexes Cp2M(SnR′3)SnPh3 or Cp2M(SnR′2Cl)SnPh3. R/Cl exchange at the tin atom is observed when an excess of the chlorostannane is used. Upon reaction of Li[Cp2MSnPh3] with Ph3PbCl only Cp2M(PbPh3)SnPh3 is formed, while a mixture of Cp2M(PbMe3)SnPh3 and Cp2M(PbMe2Cl)SnPh3 is obtained with Me3PbCl due to redistribution reactions. The structures of Cp2W(SnPh3)C(O)Ph, Cp2W(SnPh3)SntBu2Cl and Cp2W(SnPh3)PbMe2Cl were determined by X-ray structure analyses.
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    Thietane and Selenetane Complexes by Thermal Cycloaddition of Vinyl Ethers to Transition-Metal-Coordinated Thio- and Selenoaldehydes - Crystal Structure of Pentacarbonyl(7-phenyl-2-oxa-8-thiabicyclo[4.2.0]octane-S)tungsten(0)Dedicated to Professor Max Herberhold on the occasion of his 60th birthday (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1169-1175 
    Details
    ISSN: 0009-2940
    Keywords: Thioaldehyde complexes ; Selenoaldehyde complexes ; Thietane complexes ; Selenetane complexes ; Rearrangements ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pentacarbonyl(thiobenzaldehyde)tungsten und pentacarbonyl(selenobenzaldehyde)tungsten (1a and 1b) undergo a thermal [2 + 2] cycloaddition with several vinyl ethers to give highly substituted transition metal-coordinated thietanes and selenetanes. The addition is highly regio- and stereospecific. The products undergo acid-catalyzed rearrangements, which lead to thermodynamically more stable diastereomers of the thietanes and selenetanes. The stereochemistry of both addition and rearrangement was established by reaction of deuterium-labeled vinyl ethers and by reaction of the cis and trans isomers of ethyl propenyl ether. The crystal structure of the bicyclic addition product of 1a and 3,4-dihydro-2H-pyran is reported.
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    Zinc Complexes of Amino Acids and Peptides, 9[Part 8: Ref.[1].]. Coordination of Cysteine and Histidine Derivatives to the Pyrazolylborate-Zinc Unit (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1251-1257 
    Details
    ISSN: 0009-2940
    Keywords: Zinc complexes ; Cysteine ligands ; Histidine ligands ; Imidazole ligands ; Pyrazolylborate ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Highly substituted pyrazolylborate ligands TpR,Me were used to limit the coordination number of zinc towards cysteine- and histidine-derived coligands. Monodentate thiolate attachment (→ 1a-f) was achieved with N- and C-protected cysteine, monodentate carboxylate attachment (→ 3) with N-protected histidine. C-protected cysteine was found to form a five-membered N,S-chelate ring (2). While imidazole coordination with N- and C-protected histidine could not be achieved, cationic pyrazolylborate-zinc-coligand complexes [TpZn-L]+ (4a, b) were obtained for L = 2-methylimidazole. The new complexes were characterized by their spectra and three structure determinations.
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    Organmetallic Selenolates, IVPart III: Ref.[1].. Reactions of MSeW(CO)3cp (M=Li, Na) with Organodi- and -tetrahalides - X-ray Crystal Structures of C6H5CH2W(CO)3(η5-C5H 5), μ-[m-C6H4{CH2SeW(CO)3(η5-C5H5)}2], μ-[p-C6H4{CH2SeW(CO)3- (η5-C5H5)}2], and C6H5CH[SeW(CO)3(η5-C5H5)]2 (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1275-1279 
    Details
    ISSN: 0009-2940
    Keywords: Organotungsten selenolates ; 77Se NMR ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organotungsten-selenolato complexes were prepared in moderate yields by insertion of selenium into the alkali metaltungsten bonds of MSeW(CO)3cp (M = Li, Na) and subsequent reactions with the organohalides o-, m-, and p- C6H4(CH2Br)2, C6H5CHBr2, m-C6H4(CHBr2)2 and C6H5CCl3. The 77Se-NMR data of the new complexes are discussed and compared with those of related complexes derived from organomonohalides. Moreover, the X-ray crystal structures of C6H5CH2W(CO)3cp (1), μ-[m-C6H4{CH2SeW(CO)3cp}2] (3), μ-[p-C6H4{CH2SeW(CO)3cp}2] (4), and C6H5CH[SeW-(CO)3cp]2 (5) were determined. In complex (1), the W-CH2 bond length is 2.374 Å; the W-Se bond lengths in the complexes 3, 4 and 5 are all in the range 2.625-2.655 Å, corresponding to W-Se single bonds.
    Additional Material: 3 Ill.
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    Masthead (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961291101
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    Suzuki-Coupling of Cp*Ru(para-C6H4Br2) with Phenyl Boronic Acid: A Model Reaction for the Synthesis of Organometallic PolymersDedicated to Professor Günter Szeimies with gratitude on the occasion of his 60th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1323-1325 
    Details
    ISSN: 0009-2940
    Keywords: Suzuki coupling ; π Complexes, organometallic ; π Complexes, dihaloarene ; Ruthenium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of a terphenyl derivative complexed by the cationic moiety Cp*Ru+ by Suzuki coupling of [Cp*Ru(BrC6H4Br)]OTf with phenyl boronic acid under catalysis of Pd(PPh3)4 in a DME-water mixture at 85°C in quantitative yield is reported. The stable coupling product 3 was characterized by X-ray crystal structure analysis.
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    URL: http://dx.doi.org/10.1002/cber.19961291103
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    Molecular Gymnastics of Alkynes Orchestrated by Ruthenium Complexes (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1313-1322 
    Details
    ISSN: 0009-2940
    Keywords: Vinylidene complexes ; Allenylidene complexes ; Ene type reactions ; Atom economial reactions ; Reconstitutive additions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ruthenium complexes catalyze a variety of addition or isomerization reactions that are highly atom economical. Terminal alkynes react with allyl alcohols to form β,γ-unsaturated ketones that can be readily isomerized to α,β-unsaturated ketones via transient vinylidene complexes. A cyclization via a transient allenylidene complex concomitant with this addition represents a novel way to build heterocycles. Ancillary studies with these catalysts revealed an internal oxidation reduction whereby allyl alcohols are isomerized to saturated ketones and propargyl alcohols are isomerized to α,β-unsaturated carbonyl compounds. Consideration of the reaction mechanism led to a general Alder ene type reaction wherein alkynes serve as the enophile and alkenes serve as the ene component. These discoveries have led to a number of efficient total syntheses of biologically interesting targets. Mechanistic investigations into the activation of a ruthenium complex led to the discovery of a novel bis-homo-Diels-Alder reaction of 1,4-cyclooctadiene.
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    A Theoretical Study of Thionitrosyl Azide (N3—N=S), Thiazyl Azide (N3—S≡N) and Nitrosyl Azide (N3—N=O) (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1373-1377 
    Details
    ISSN: 0009-2940
    Keywords: Thionitrosyl azide ; Thiazyl azide ; Nitrosyl azide ; Tetranitrogen sulfide ; Calculations, ab initio ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Stimulated by the recent detection of nitrosyl azide (N3—N=O), we investigated the stability of the sulfur analogues thionitriosyl azide (N3—N=S) and thiazyl azide (N3—S≡N) by using ab initio MO calculations up to the QCISD(T)/6-311+G(d)//QCISD/6-311G(d) + ZPE level. Both azides have a similar energy content. While thionitrosyl azide is not stable with respect to N2 elimination, thiazyl azide resists to this process by an energy barrier of about 110 kJ/mol. The NS and N3 fragments resulting from homolytic cleavage lie about 100 kJ/mol above the azides. The five-membered ring is thermodynamically much more stable than both azides but kinetically unstable with respect to cheletropic decomposition yielding N2S + N2. Overall, trans-thiazyl azide is the most likely candidate for experimental observation of, for example, the reaction of NS+ salts with the azide anion. IR wavenumbers of the azides were also predicted.
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    Synthese, Eigenschaften und Kristallstrukturen der Titan(III)-Amido-Komplexe Ti[N(SiMe3)2]3, [TiCl2{N(SiMe3)2}(THF)2] und [Na(12-Krone-4)2][TiCl2{N(SiMe3)2}2] (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1401-1405 
    Details
    ISSN: 0009-2940
    Keywords: Amido complexes ; Titanium(III) compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Syntheses, Properties, and Crystal Structures of the Titanium(III) Amido Complexes Ti[N(SiMe3)2]3, [TiCl2{N(SiMe3)2}(THF)2], and [Na(12-Crown-4)2][TiCl2{N(SiMe3)2}2]TiCl3(THF)3 reacts with NaN(SiMe3)2 to furnish [TiCl2{N(SiMe3)2}(THF)2] (1), whereas in the presence of 12-crown-4 the ionic amido complex [Na(12-crown-4)2][TiCl2{N(SiMe3)2}2] (5) is obtained besides [Na(12-crown-4)2][TiCl4(THF)] (4). On the other hand, the titanium(III) amido complex Ti[N(SiMe3)2]3 (2), the crystal structure of which was solved, reacts with NaN(SiMe3)2 in the presence of 12-crown-4 with deprotonation of one of the methyl groups to give the carbometalated complex [Na(12-crown-4)2][Ti{N(SiMe3)2}2{N(SiMe 3CH2)}] (3).
    Additional Material: 4 Ill.
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    Komplexe von Halogenid-Ionen mit Diiodacetylen. Die Kristallstrukturen von PPh4[X(I-C≡C-I)2] mit X = Cl, Br, I (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 259-262 
    Details
    ISSN: 0009-2940
    Keywords: Halide complexes of diiodacetylene ; Crystal structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complexes of Halide Ions with Diiodoacetylene. The Crystal Structures of PPh4[X(I-C≡C-I)2] with X = Cl, Br, IThe complexes PPh4[X(I-C≡C-I)2] with X = Cl (1), Br (2), and I (3) have been prepared from the phosphonium salts PPh4X and 1-C≡C-I in dichloromethane solutions. 1-3 form colourless crystals, which according to crystal structure analysis crystallize isotypically in the space group P421m with two formula units per unit cell. The diiodacetylenes are coordinated by the halide ions X- in a distorted tetragonal fashion, the I-C≡C-I molecules being in μ2-bridging function. Thus, a polymeric anionic network [X(I-C≡C-I)2]nn- with a layered structure results.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19961290224
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    Phosphorus Analogs of Bipyridines: Their Synthesis and Coordination ChemistryMost of the work described in this review was done in the laboratory of the authors. The help of many dedicated coworkers and colleagues, whose names are cited in the references, is acknowledged. The unpublished X-ray crystal structure analyses were performed by our colleague Dr. Louis Ricard. Over the years, this program has been supported by CNRS, SNPE and Ecole Polytechnique. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 263-268 
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    ISSN: 0009-2940
    Keywords: 2-(2-Pyridyl)phosphinines ; 2,2′-Biphosphinines ; Transition metals ; Biphosphinine chelates ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and coordination chemistry of 2-(2-pyridyl)-phosphinines and 2,2′-biphosphinines are reviewed. A noteworthy series of homoleptic complexes of 4,4′,5,5′-tetramethyl-2,2′-biphosphinine (tmbp) with Cr(0), Mo(0), Wo(0) and Ni(0) are described. A [Cu(bpy)(tmbp)]+ cationic polymer has been characterized by X-ray analysis. Ruthenium, manganese and rhenium chelates were also obtained. With Mn2(CO)10, a (tmbp)-Mn2(CO)6 complex is formed where tmbp acts as an eight electron donor.
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    URL: http://dx.doi.org/10.1002/cber.19961290303
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    Organometallic Group-13 Metal Complexes of d-Block Elements, XIVPart XIII: See ref.[10].. Intramolecularly Base-adduct-stabilized Transition-metal-substituted Indanes: Synthesis and Spectroscopic Characterization, Structure of (η5-C5H5)(CO)Ni—InBr2(NC7H13) (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 297-303 
    Details
    ISSN: 0009-2940
    Keywords: Transition-metal indium complexes ; Nickel-indium bonds ; Intramolecular Lewis base adducts ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of InBr/InBr3 or InBr/BrIn[(CH2)3NMe2]2 with the transition metal dimers [L(CO)nM]2 {L = CO, Cp, C5H4[(CH2)2NMe2]; M = Fe, Co, Ni; n = 1-3} in THF or dioxane gives in almost quantitative yield the transition metal indium complexes L(CO)nM—InBr2(Do) (Do = THF, NC7H13) and L(CO)nM—In[(CH2)3NMe2](Br) respectively. The new compounds were characterized by elemental analysis, infrared v(CO) spectroscopy, NMR, and mass spectrometry. An X-ray single crystal structure determination of (η5-C5H5)(CO)-Ni-InBr2(NC7H13) (1a) revealed a short Ni-In bond of 246.3(1) pm.
    Additional Material: 3 Ill.
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    Improved Access to {[ω-(Phosphanyl)alkyl]cyclopentadienyl}cobalt(I) Complexes: Decomplexation of the Phosphane Arm; Alkyne Complexes; Synthesis of Mononuclear Vinylidenecobalt(I) Complexes (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 319-325 
    Details
    ISSN: 0009-2940
    Keywords: {[ω-(Phosphanyl)alkyl]cyclopentadienyl}cobalt(I) ; Cobalt complexes ; Bidentate ligand ; Alkynes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An improved synthesis of [(2-phosphanylethyl)cyclopenta-dienyl]cobalt(I) chelate complexes is presented, in which the paramagnetic chloride 3 is a precursor of the ethene complex 4. The latter readily undergoes ligand exchange reactions which in the case of bidendate reagents (1,5-cyclooctadiene, 1,2-bis(diisopropylphosphanyl)ethane, 2,2′-bipyridine, nor-bornadiene) cause a decomplexation of the phosphane arm at room temperature with formation of 7, 5, 6, 8. The ethene ligand in 4 can be replaced by alkynes under equally mild reaction conditions (formation of 9, 11 - 16). The reaction with ethyne results in the formation of vinylidene complex 10. The yields of the reactions with nonaromatic alkynes could be improved by treating 3 with the alkyne in the presence of sodium amalgam. The unsubstituted vinylidene complex 10 and its tert-butyl derivative 17 were obtained by this route in 38 and 40% yield, respectively.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19961290312
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    Cäsium-Fluor-Vierringe als Strukturmotiv in Cäsium-Triorganofluorometallaten der Gruppe 13Herrn Prof. Dr. Ekkehard Fluck zum 65. Geburtstag gewidmet. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 355-359 
    Details
    ISSN: 0009-2940
    Keywords: Aluminium compounds ; Gallium compounds ; Indium compounds ; Trimethylfluoro metalates ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cesium-Fluorine Four-Membered Rings as Structural Motive in Cesium Triorganofluoro Metalates of Group 13The reactions of AlMe3, GaMe3, and InMe3 with CsF in acetonitrile furnish the corresponding trimethylfluoro metalates Cs[Me3MF] (1: M = Al, 2: M = Ga, 3: M = In). The salt-like compounds 1 - 3 were characterized by NMR, IR, and MS techniques as well as by X-ray structure analysis. Cs2F2 four-membered rings are the structure-dominating units in all three compounds. Compound 1 consists of puckered layers of weakly associated Cs2F2 rings parallel to (100), while the four-membered rings in 2 form infinite ladder-type chains. The Cs-F rings in 3 build up a heterocubane with a Cs4F4 core by ring stacking.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19961290317
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    (tert-Butoxy)aluminium and -gallium HydridesDedicated to Prof. H. W. Roesky on the occasion of his 60th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 381-384 
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    ISSN: 0009-2940
    Keywords: Alanes, tert-butoxy- and bis(tert-butoxy)- ; Gallanes, tert-butoxy- and bis(tert-butoxy)- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structures obtained by X-ray methods of (tert- butoxy)alane and -gallane (tBuOMH2) are isotypic and are composed of discrete centrosymmetric dimers. The dimers arise from almost symmetrical Al—O—Al [1.810(3), 1.815(3) Å] and Ga—O—Ga [1.902(9), 1.908(9) Å] bridges forming a central rhombohedral four membered M2O2 cycle [O—Al—O 81.0(2)°, O—Ga—O 78.6(5)°] with the metallic atoms in a distorted tetrahedral environment. When one of the hydride ligands on the metals is further substituted by tert-butoxy, the formation of (tBuO)2AlH and (tBuO)2 GaH is observed. These two compounds crystallize in different lattices and space groups, but they are nevertheless very similar in their structure: the centrosymmetric M2O2 cycle is maintained [Al—O 1.817(3), 1.817(3) Å; Ga—O 1.904(4), 1.907(4) Å] As expected, the terminal Al-O [1.675(3) Å] and Ga—O [1.783(4) Å] distances are considerably shorter than the bridging ones.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19961290403
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    Compounds of Germanium and Tin, 18Part 17: Ref.[1].. Cleavage Reactions of Hexa-tert-butylcyclotrigermane: Racemate versus Conglomerate CrystallizationDedicated to Professor Marianne Baudler on the occasion of her 75th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 401-404 
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    ISSN: 0009-2940
    Keywords: Germanium ; Trigermanes ; Germylene ; Trapping reactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of hexa-tert-butylcyclotrigermane (3) with CCl4, Br2, and I2 furnishes the correspondingly substituted 1,3-dichloro- (4), 1,3-dibromo- (5), and 1,3-diiodotrigermanes (6). The symmetries of the molecules of 5 and 6 are very similar (point group C1) revealing gauche-anti conformations and different Ge—Ge bond lengths. However, while 5 crystallizes as a racemate, 6 forms a conglomerate of enantiomerically pure crystals. The X-ray structure analysis of the 1,3-dimethyltrigermane (7) derivative, derived from 6 by a sequence of metalation and methylation reactions, reveals more symmetrical molecules of the point group C2 which also crystallize as a racemate. Irradiation of 3 leads to tetra-tert-butyldigermene (8) and di-tert-butylgermylene (9) which could be trapped by addition and cycloaddition reactions with selenium, tellurium, and 3,5-di-tert-butyl-1,2-benzoquinone.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19961290407
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    The chemistry of metallacyclic alkenylcarbene complexes, 3Part 2: Ref.[2].. C=C bond formation with carbon nucleophiles. stereoselective dienylation of lithium enolates and cuprates and a novel cascade synthesis of highly substituted cyclopentenones from lithium acetylides (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 427-433 
    Details
    ISSN: 0009-2940
    Keywords: Carbene complexes ; Metallacycles ; Claisen rearrangement ; Cascade reaction ; Cyclopentenones ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cationic ferracyclic carbene complexes 1 react with carbon nucleophiles like lithium enolates and organocuprates to give the corresponding 4-substituted 1, (3E)-diene tricarbonyl-iron complexes 6 and 9. The reaction is thought to proceed by initial attack on the allyl terminus and subsequent ferra Claisen-Ireland rearrangement of the intermediate (η2 alkene)carbene complex 4. This rationale is supported by the isolation and characterisation of analogous aminooxocarbene derivatives 8. With sterically demanding enolates products 6 are formed in diastereomeric ratios of up to 90:10, thus demonstrating the inductive power of the chiral metallacycle in 1. Lithium acetylides as carbon nucleophiles react with 1 according to a novel cascade to give regio- and stereospecifically 2,5,5-trisubstituted-cyclopentenones 10 suggesting a concerted formation of four C=C bonds together with a CO insertion and a formal carbene transfer step.
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    Zinc complexes of the N,N,S ligand (mercaptophenyl)(picolyl)amine (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 435-440 
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    ISSN: 0009-2940
    Keywords: Zinc complexes ; Sulfur and nitrogen ligands ; Structure and bonding ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The zinc complex chemistry of the tridentate thiol ligand N- (2-mercaptophenyl)(2-picolyl)amine (MPPAH) differs considerably from that of the aliphatic analogue N-(2-mercaptoethyl)(2-picolyl)amine reported previously. This is due to the lower basicity and hence bridging tendency of its aromatic thiolate function. With zinc salts of oxo anions the 1:1 complexes (MPPA)ZnX (1a-c: X = ONO2, OAc, OBz) are formed which according to spectroscopic data are monomeric while the halide (MPPA)ZnBr (2) seems to be polymeric. In the absence of coordinating anions the monomeric 2:1 complex (MPPA)2Zn (3) results which according to a crystal structure determination contains tetrahedral zinc coordinated by one MPPA ligand in a tridentate fashion while the other is only monodentate and sulfur-bound. A similar N2S2 coordination can be deduced for the 1:1:1 complex (MPPA)Zn(STrt) (4) resulting from ZnEt2, MPPAH and triphenylmethanethiol.
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    Reactions of diaminophosphenium and 1,3,2-diazaphospholenium triflates with silver saltsDedicated to Professor Dr. Marianne Baudler on the occasion of her 75th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 465-469 
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    ISSN: 0009-2940
    Keywords: Phosphenium cations ; Silver complexes ; 31P, 109Ag NMR shift correlation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of bis(diisopropylamino)phosphenium triflate (1[CF3SO3]) with silver salts AgY [Y- = CF3CO2- (2a), CF3-SO3- (2b), CH3CO2- (2c)] affords neutral complexes [{(iPr2N)2(Y)P} Ag(OSO2CF3)] (3a-c). While 3a, c are stable up to ambient temperature, 3b is only stable at low temperature and in equilibrium with the cation 1. The constitution of 3a-c was derived from multinuclear (1H, 13C, 31P, 109Ag) NMR spectra. Compound 3a was further studied by X-ray single-crystal diff ractommetry which showed the presence of dimeric units with μ2-bridging triflate ligands and three-coordinate silver atoms with a planar T-shaped coordination geometry. Reaction of 4-chloro-1,3-bis(2,6-dimethylphenyl)-1,3,2-diazaphospholenium triflate (4[CF3SO3]) with 2a, c affords equilibrium mixtures whose 31P- and 109Ag-NMR spectra suggested the presence of silver complexes 5a, c with constitutions similar to those of 3a, c besides unreacted cation 4. No reaction was observed between 4[CF3SO3] and 2b. A common mechanism accounting for the different outcome of the individual reactions will be discussed.
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    Synthesis, Structure, and Magnetic Properties of a 2,2-Dipyridyl-2,5-dihydro-imidazole-1-oxyl-(L-)Bridged Disilver Complex [Ag2L2](SbF6)2: A Four-Membered Ring from two Ag(I) Ions and two Imine Nitrogen AtomsDedicated to Professor Marianne Baundler on the occasion of her 75th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 571-573 
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    ISSN: 0009-2940
    Keywords: Nitroxide radical ; Silver(I) complex ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of 2,5-dihydro-4,5,5-trimethyl-2,2-di-2-pyridyl-imidazole-1-oxyl (L) with AgSbF6 gives the complex [Ag2L2]2+[SbF6-]2 which was characterized by X-ray diffraction. - The complex (a biradical) forms a four-membered ring with two Ag(I) ions and two imine nitrogen atoms of the imidazolines with a relatively short Ag - Ag distance [2.839(2) Å]. Magnetic measurements indicate that two nitroxide radicals are slightly coupled.
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    URL: http://dx.doi.org/10.1002/cber.19961290515
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  • 87
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    Silver(I) Complex of a Crown Thioether Retaining the Transoid S-C-C-S Ligand ConformationDedicated to Prof. Marianne Baudler on the occasion of her 75th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 581-584 
    Details
    ISSN: 0009-2940
    Keywords: Crown thioether ; Silver(I) complex ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crown thioether 3 with the novel diisopropylidene building block was synthesized by an S′N cyclization reaction of 2,7-dichloro-2,7-dimethylocta-3,5-diyne (1) with 3-thia-pentane-1,5-dithiol (2). Ligand 3 shows all the sulfur centers in exodentate positions. Reaction of 3 with Ag1 triflate and triphenylphosphane yielded the tetrahedral complex 4, which shows unique spectroscopic data in solution. Crystallization furnished two different crystal forms (4a and 4b). Both are different conformers which are stable in the solid state. 4a exhibits a crown-like structure of the thioether ligand with cisoid S—C—C—S chains. To our knowledge 4b is the first silver(1) complex with a crown thioether retaining the tran-soid S—C—C—S conformation in the metal complex.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19961290517
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  • 88
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    The Chemistry of Metallacyclic Alkenylcarbene Complexes, 4Part 3: Ref.[36].. Unsaturated Metallacyclic Carbene Complexes as Flexible Tools in Organic Synthesis. Novel Rearrangement and Cascade Pathways to Functionalized Alkadienes, Carbo-, and Heterocycles (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 595-602 
    Details
    ISSN: 0009-2940
    Keywords: Carbene complexes ; Organoiron compounds ; Metallacycles ; Rearrangements ; C — C coupling ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cationic metallacyclic carbene complexes of iron and cobalt bearing a terminal η3-allyl ligand are susceptible to nucleophilic attack at different sites depending on the particular set of substituents, the central metal fragment, and the nucleophile. Attack of enolates, cuprates, acetylides, or heteroatom nucleophiles like phosphanes at the metallacyclic perimeter of the iron complexes 18 provides an easy access to unsaturated organic products like 1,2- or 1,3-dienes, δ-lactones, and functionalized cyclopentenones through novel rearrangement or cascade pathways. Synthetic applications are described; factors governing reactivity/selectivity are discussed; X-ray analytical structures of novel metallacycles are provided.
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    URL: http://dx.doi.org/10.1002/cber.19961290602
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  • 89
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    [Bis(phosphonio)isophosphindolide]silver ComplexesDedicated to Professor Dr. Rolf Appel on the occasion of his 75th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 337-345 
    Details
    ISSN: 0009-2940
    Keywords: Bis(phosphonio)isophosphindolide cations ; Silver complexes ; 31P NMR ; 109Ag NMR ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The outcome of reactions of bis(phosphonio)isophosphindolide salts 1[X] and 6[X] (X- = Cl-, Br-, CF3SO3-) with silver salts AgY (Y- = CF3SO3-, CF3CO2-, CH3CO2-, 1/2 SO4-) depends strongly on the available anions X, Y. If X-, Y- = CF3SO3-, both mononuclear and dinuclear silver complexes are formed which exhibit either μ1,μ1(P) or μ2,η1(P) coordination of the cations 1, 6 to one or to both metals. In solution, dynamic equilibria between both types of products and free 1, 6 were detected by 31P-NMR spectroscopy. Mononuclear (4a, 7) and dinuclear (5a, 8) complexes were isolated as solvates with CHCl3 or THF. If X-, Y- = CF3CO2, only equilibrium mixtures between the free ligands and silver complexes and no isolable products were obtained. 31P-NMR investigations revealed a preference for the formation of dinuclear complexes. Anion metathesis and precipitation of AgX were observed for X- = Cl-, Br-. No coordination of 1, 6 to Ag+ took place in the case of Y- = CH3CO2-, SO42-. The formed complexes were characterised in solution by 31P- and in part by 109Ag-NMR spectroscopy. Complexes 7, 8 were further studied by single crystal X-ray diffraction which revealed the presence of a THF molecule coordinated to silver in both cases. The μ2-coordinated cation 1 is the only bridging ligand in 8, whereas the presence of additional μ2-CF3CO2 ligands was deduced from the results of 31P,31P EXSY measurements in the case of the trifluoroacetato complexes.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19961290315
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  • 90
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    The Chemistry of Arsenic—Carbon Multiple Bonds: Arsaalkenes and ArsaalkynesDedicated to Professor Kurt Dehnicke on the occasion of his 65th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 367-379 
    Details
    ISSN: 0009-2940
    Keywords: Arsaalkene chemistry ; Arsaalkynes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The present article gives an account of the synthesis and structure as well as the spectroscopic and chemical properties of arsaalkenes R1As=CR2R3 and arsaalkynes RC≡As. Arsaalkenes are significantly less stable and more reactive than the corresponding phosphaalkenes. Only one kinetically stabilized arsaalkyne has been described so far.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19961290402
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  • 91
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    Reaction of the Alkylindium(I) Compound In4[C(SiMe3)3]4 with Octacarbonyldicobalt: Bridging of the Co—Co Bond by one or two In—C(SiMe3)3 GroupsDedicated to Prof. Dr. Kurt Dehnicke on the occasion of his 65th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 397-400 
    Details
    ISSN: 0009-2940
    Keywords: Tetraindane(4) ; Indium(I) ; Co—Co bond ; Indium alkyl bridge ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: tetrahedra-Tetrakis[tris(trimethylsilyl)methyl]tetraindane(4) (1) reacts with octacarbonyldicobalt to yield two products, depending on the stoichiometric ratio of the starting compounds: By replacement of one bridging carbonyl group a dicobalt monoindium derivative 2 is formed, which contains a Co—Co bond [256.81(5) pm] bridged by one carbonyl and one monoalkylindium group. While 2 is a monomer in benzene solutions, it dimerizes in the solid state by an interaction of the oxygen atom of the bridging carbonyl group to the coordinatively unsaturated In atom of a second molecule across a center of symmetry. Another compound (3) is formed by the replacement of both bridging carbonyl ligands, which exhibits a strongly distorted Co2In2 tetrahedron with normal Co—In bond lengths of 253.44(6) pm, but long Co—Co [280.14(6) pm] and In—In distances [336.18(6) pm].
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19961290406
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  • 92
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    The effect of substituting phosphorus for a ring carbon atom in the valence isomers cyclobutene, bicyclobutane, and 1,3-butadiene. a quantum-chemical investigation (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 419-425 
    Details
    ISSN: 0009-2940
    Keywords: Cyclobutene ; Bicyclobutane ; 1,3-Butadiene ; Phosphorus substitution ; Relative energies ; Quantum chemical investigations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclobutene, bicyclobutane, and 1,3-butadiene are valence isomers within the concept of the Woodward-Hoffman rules. According to thermochemical considerations and in agreement with energy optimized quantum-chemical calculations at the ab initio RHF and MP2/6-31G(d,p) levels bicyclobutane is the least and 1,3-butadiene the most stable valence isomer. Phosphorus substitution exerts a considerable effect on the relative stabilities of the various valence isomers. Bicyclobutanes containing phosphorus atoms in the bridgehead positions are considerably more stable than the other phosphorus-substituted valence isomers. This conclusion was confirmed by an analysis of the natural bond populations.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19961290410
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    Paramagnetic Planar Complexes of NiII: Influence of R and R′ on the Formation, Coordination Geometry and Magnetic Properties of Phosphinic Amidato Bischelates [R2P(O)NR′]2Ni (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 551-555 
    Details
    ISSN: 0009-2940
    Keywords: Paramagnetic planar complexes of NiII ; Phosphinic amidato ligands ; NMR spectroscopy ; Magnetic measurements ; Vis spectra ; Crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: After a brief review of previous work the results of the metathesis reaction between Ni(dme)Br2 and R2P(O)NR′Li [R = tBu, iPr, Ph; R′ = Et, Pr, iPr, (±)-sBu, tBu, tPen, Cy, Ph, (-)-α-methylbenzyl = Mb, 1-adamantyl = Ad] are reported. Complex formation occurred only with lithiated amides of tert-butylphosphinic acid, and bischelates [tBu2P(O)NR′]2Ni were obtained when R′ = sBu, Mb, tPen, Ad (1d - g). With R′ = Et, Pr bischelation was incomplete. Vis spectroscopy showed the paramagnetic compounds 1d - f to be planar in the solid state but tetrahedral in solution. 1g is tetrahedral in both phases. The planar structure of 1f was confirmed by X-ray single-crystal analysis (monoclinic, space group P21/n). The magnetic moments μeff of 1d, e, g are ca. 3.2-3.5 μB in both phases and the Curie-Weiss law is obeyed in the range 293-183 K. The same is valid for dissolved 1f. The μeff values of solid 1f are however, strongly temperature-dependent, varying from 1.38 to 0.55 μB (300-90 K). NMR data (31P, 1H, 13C) are reported. Obviously, a favorable combination of electronic and steric factors of substituents R and R′ produces with ligands [R2P(O)NR′]- the donor quality necessary for bischelation as well as the singular field strength required for the formation of planar paramagnetic species. As the combination of paramagnetism and planarity is bound to the solid state, lattice energy effects may be finally decisive for this unique constellation of tetracoordinated NiII complexes.
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    Metal-Catalyzed Oxidations, 4Part 3: Ref.[1].. The Reaction of Molybdenumperoxo Complexes with Brønsted and Lewis Acids (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 575-580 
    Details
    ISSN: 0009-2940
    Keywords: Molybdenum complexes ; Peroxo complexes ; Catalysis ; Olefin epoxidation ; Proton transfer ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: NMR studies of the reaction of complexes of the type (L-L)MoO(O2)2 (L - L= bidentate ligand) with strong Brønsted and Lewis acids prove that protons are transferred preferentially to an η2-peroxo and not to the oxo ligand. This behavior in proton transfer reactions is one critical point of the catalytic activity of such complexes in olefin epoxidation. EH calculations on the model complex (NH3)2MoO(O2)2 support the spectroscopic investigations.
    Additional Material: 7 Ill.
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  • 95
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    Twofold Insertion of Isocyanides into the Ga—Ga Bond of Tetrakis[bis(trimethylsilyl)methyl]digallane(4) (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 897-901 
    Details
    ISSN: 0009-2940
    Keywords: Gallium-Gallium bond ; Isocyanide insertion ; 1,4-Diazabutadiene derivatives ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetrakis[bis(trimethylsilyl)methyl]digallane(4) (1) reacts with tert-butyl or aryl=isocyanides [aryl = phenyl, o-methylphenyl, o-methoxyphenyl, p-methoxyphenyl) by a twofold insertion of the central carbon atoms into the Ga-Ga bond and formation of C-C single bonds. 1,4-Diazabutadiene derivatives bound to two R2Ga groups are formed (2-6), which in contrast to an aluminium analog exhibit only weak interactions between the imine nitrogen atoms and the coordinatively unsaturated gallium atoms as indicated by NMR spectroscopy and the long Ga-N distances in the molecular structures of three products: 2 (R = C6H5), 4 (R = o-MeOC6H4), and 6 (R = CMe3).
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19961290804
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    Semiconductor-Catalysed Photoaddition: γ,δ-Unsaturated Amines from Cyclopentene and Schiff BasesHeterogeneous Photocatalysis, XIV. - Part XIII: Ref.[10b].Dedicated to Professor Max Herberhold on the occasion of his 60th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 925-932 
    Details
    ISSN: 0009-2940
    Keywords: Cadmium sulfide ; Paired photoelectrolysis ; γ,δ-Unsaturated amines ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Irradiation of methanolic cadmium sulfide suspensions in the presence of Schiff bases and cyclopentene opens an easy access to new γ,δ-unsaturated amines. Their formation can be described as a kind of paired photoelectrolysis induced by the photogenerated electron-hole pair trapped at reactive surface sites of CdS. At the reductive site the imine is converted to an α-aminobenzyl radical by a proton-coupled electron transfer, while at the oxidative site cyclopentene is transformed to the cyclopentenyl radical through deprotonation of the intermediate radical cation. C-C coupling of these radicals affords the addition products. Competitive dimerisation of the radicals produces hydrodimers of the imines and dehydrodimers of the olefin, as demonstrated in the case of 1-phenylcyclohexene. Using optical active imines, we found no significant diastereoselectivity. In the absence of an olefin the alcoholic solvent was added to the imine. The molecular structure of one hydrodimer was resolved by X-ray analysis. When CdS/Pt was used as photocatalyst, hydrolysis products of the imine were formed, suggesting involvement of an intermediate OH radical.
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    URL: http://dx.doi.org/10.1002/cber.19961290808
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    Organoamido- and Aryloxo-lanthanoids, 14Part 13: Ref.[1].. Organometallic Compounds of the Lanthanoids, 106Part 105: Ref.[1].. Synthesis and Characterisation of Complexes of Lanthanoid Pyrazolates with 1,2-Dimethoxyethane and the X-Ray Structures of (1,2-Dimethoxyethane-O1:O2)(1,2-dimethoxyethane-O1)tris(3,5-diphenylpyrazolato)erbium(III) and catena-Poly[tris(3,5-di-tert-butylpyrazolato)-μ-(1,2-dimethoxyethane-O1:O2)-neodymium(III)] (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 953-958 
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    ISSN: 0009-2940
    Keywords: Lanthanum complexes ; Neodymium complexes ; Erbium complexes ; Pyrazolate, 3,5-di-tert-butyl-, complexes of ; Pyrazolate, 3,5-diphenyl-, complexes of ; 1,2-Dimethoxyethane, complexes of ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complexes [Ln(Ph2pz)3 (DME)2] and [Ln(tBu2pz)3 (DME)] (Ln = La, Nd, Er; Ph2pzH = 3,5-diphenylpyrazole; tBu2pzH = 3,5-di-tert-butylpyrazole; DME = 1,2-dimethoxyethane) have been prepared by reaction of the lanthanoid metal with bis(pentafluorophenyl)mercury and the pyrazole in DME. The molecular structures of [Er(Ph2pz)3 (DME)2] (3) and [Nd(tBu2pz)3 (DME)]∞ (5) have been determined by X-ray diffraction. Complex 3 has nine-coordinate Er with three chelating Ph2pz ligands and one chelating and one η1-bound DME. There is a trigonal prismatic arrangement of the oxygen donors and the centres of the N - N bonds. 5 was found to be a linear polymer with transoid DME ligands bridging Nd(tBu2pz)3 units in a novel manner. The centres of the N - N bonds (which are essentially coplanar with Nd), and the oxygen donor atoms adopt an arrangement intermediate between trigonal-bipyramidal and square-pyramidal [O - Nd - O 153.5(2)°].
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    URL: http://dx.doi.org/10.1002/cber.19961290812
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    Control of Regioselectivity in the Transition-Metal-Catalysed Conjugate Additions of Alkylaluminium Compounds and Methyltitanium Ate Complexes to Androsta-1,4-diene-3,17-dione (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 963-966 
    Details
    ISSN: 0009-2940
    Keywords: Steroids ; Androsta-1,4-diene-3,17-dione ; Conjugate addition ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By a variation of the nature of the reagent system conjugate addition to the cross-conjugated steroidal dienone 1 occurs selectively either at C-1 or at the sterically hindered C-5. With Me3Al or Me4AlLi in the presence of catalytic amounts of Cu1 salts, a high regioselectivity (up to 97:3) in favour of position 1 is achieved. Application of ate complexes of aluminium and titanium in the presence of Ni(acac)2 as catalyst, however, leads to a reversal of the regioselectivity in favour of position 5 (up to 11:89). Aluminium and titanium ate complexes are efficient reagents in the Ni(acac)2-catalysed conjugate addition to sterically hindered enones.
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    URL: http://dx.doi.org/10.1002/cber.19961290814
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    Komplexe mit Metall-Phosphor-Dreifachbindungen als mögliche Intermediate der Umsetzungen von Chlorophosphiniden-Komplexen mit Metallaten verschiedener ÜbergangsmetalleHerrn Professor Max Herberhold zum 60. Geburtstag gewidmet. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 973-979 
    Details
    ISSN: 0009-2940
    Keywords: M2P2 tetrahedral complexes ; Phosphido ligand complexes as intermediates ; Ni2P4O distorted prismane framework ; CO incorporation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complexes with Metal-Phosphorus Triple Bonds as Possible Intermediates in the Reactions between Chlorophosphinidenes and Metalates of Various Transition MetalsThe reaction of [{M′(CO)5}2PCl] (M′ = Cr, W) with various metalates ([Cp′Mo(CO)3]-, [Cp * Ni(CO)]-, [Cr2(CO)10]2-) yields the M2P2 tetrahedral complexes [(MLn)2(μ,η2- P2){M′(CO)5}2] (MLn = Cp*Ni, M′= Cr (1), W (2); MLn = Cp′Mo(CO)2, M′ = Cr (4); Cp* = η5-C5Me5, Cp* = η5C5H3tBu2) and the cyclo-P4 compound [{Cr(CO)4}(η4-P4){Cr(CO)5}4] 6. As side products the distorted prismane [(Cp*Ni)2{μ4,η4-(P2-O-P2)}{W(CO)5}2] 3 and the diphosphino-methanone complex [{Cp′Mo(CO)2}2{μ4η2-PC(O)P}-{Cr(CO)5}2] 5 are formed. The complexes are characterised by NMR, IR, MS, and X-ray structure analysis (1-5). Studying the reaction pathway provided evidence of phosphido intermediates of the type [LnM≡P→M′Ln].
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    Chirale Tripod-Liganden mit Phosphit-Donorgruppe: Synthese und KomplexchemieHerrn Prof. Dr. Kurt Dehnicke zum 65. Geburtstag gewidmet. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 697-713 
    Details
    ISSN: 0009-2940
    Keywords: Chiral tripodal ligands ; Tripod rhodium complexes ; Chiral diphosphanes ; Chiral phosphites ; Ring opening of epoxides ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chiral Tripodal Ligands Bearing a Phosphite Donor Group: Synthesis and Coordination ChemistryThe mechanism of the reaction of epichlorohydrine (H-CH2Cl) (1) with lithium phosphides is analysed. A neighbouring-group mechanism has been found to be the essential driving force in this reaction. Monophosphanyl alcohols such as HOCH(CH2P(Ph)2)(CH2Cl) (2) and epoxides (Ph)2PCH2- (3) are characterized as intermediates. The mechanism leads to a rapid one-pot method for the synthesis of chiral racemic as well as enantiomerically pure bis(phosphanyl) alcohols HOCH(CH2PR2)(CH2PR2′) (4). The resulting bis(phosphanyl) alcohols 4 react easily with X2PCl (X = Cl; Ph; or X2 = 1,2-ethanedioxy-2,2′-biphenyldiyldioxy-) to yield the mixed donor group tripodal ligands X2POCH(CH2PR2)(CH2PR′2) (5, 6) containing both phosphite, phosphinite or phosphorodichloridite and phosphane donor groups. The identity of these compounds were proved by 1H-, 31P- and 13C-NMR spectroscopy, mass spectra, microanalysis as well as X-ray analysis. The coordination capabilities of these novel ligands are demonstrated by the synthesis and characterization of a (cyclooctadiene)rhodium complex {[(5c)Rh(I)COD]PF6} (7) of the ligand 5c, exhibiting the typical hetero-bicyclooctane tripod metal cage of this type of tripod complexes.
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    URL: http://dx.doi.org/10.1002/cber.19961290617
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