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  • 1
    ISSN: 0009-2940
    Keywords: Palladium ; Phosphanes ; Catalysis ; Cyclopalladation reaction ; Metallacycles ; CH activation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to synthesize chiral palladacycles for stereoselective C-C coupling reactions we studied the cyclopalladation of P-chiral phosphanes 2 and 3. New palladium complexes of the type L2PdX2 (6, 8) and LXPd-μ-X2-PdXL (5, 9, X = Cl; L = 2, 3) were isolated. A detailed study of the reactivity of all intermediates towards cyclopalladation proved the mechanism of cyclometalation reactions of o-tolylphosphanes for the first time. Different deuteration experiments clearly demonstrated the higher reactivity of dimeric palladium complexes towards metalation compared to monomeric species. In agreement with this observation only 5 and 9 gave the cyclopalladated products 4 and 10 as revealed by FAB mass spectrometric investigations. Under the described reaction conditions the synthesis of the corresponding palladacycles 4, 10 is not possible because cyclometalation is a reversible process with LXPd-μ-X2-PdXL as thermodynamic more stable products. The results demonstrate the importance of free coordination sites on the metal atom for cyclometalation reactions or more general CH activation processes.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 21 (1982), S. 117-130 
    ISSN: 0570-0833
    Keywords: Fischer-Tropsch synthesis ; Catalysis ; Cluster compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Fischer-Tropsch Synthesis counts among the industrial-scale processes having a versatile and broad product range, and has for decades offered the most attractive possibility for the use of coal as a source of heating oil and fuels. This conceivably simple reaction, the catalytic hydrogenation of carbon monoxide, generally leads to simple hydrocarbons as well (i.e. short chain olefins) that have been sought as chemical feedstocks since the oil crisis of the seventies, but fails to provide the large-scale, economic process required, due in large part to the minimal selectivity of traditional Fischer-Tropsch processes. In an effort to solve this problem current research in this sector is concerned not only with the optimization of old and the development of new catalytic systems, but also increasingly with the elucidation of numerous relevant reaction mechanisms. This article will discuss, from the viewpoint of an organometallic chemist, the significance of typical model reactions, both with regard to some fundamental aspects of synthesis gas chemistry, and in comparison with previous views concerning the mechanism of the Fischer-Tropsch Synthesis. The importance of various unique classes of complexes that have been studied in the context of Fischer-Tropsch chemistry is also evaluated with regard to their importance in the synthesis of hydrocarbons from carbon monoxide and hydrogen. It emerges that the primary steps of the reductive oligomerization of carbon monoxide are best described by the carbide/methylene mechanism, as originally proposed by Hans Fischer and Franz Tropsch.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0570-0833
    Keywords: Rhenium ; Catalysis ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Homogeneous catalysis as the major industrial outlet of organometallic basic research has been enjoying great benefit from organotransition metal species that promote bond forming between hydrocarbon fragments. Most of the commercially important processes that serve to produce large-volume organic feedstock chemicals such as linear α-olefins (Shell Higher Olefins Process), linear aldehydes (hydroformylation), acetaldehyde (Wacker-Hoechst), acetic acid (Monsanto), adiponitrile (DuPont hydrocyanation of butadiene) operate at low-valent metal centers. It is thus hardly surprising that by far the most part of organometallic research during the past few decades has been directed towards an understanding and the improvement of these catalytic reactions as well as towards the related stoichiometric chemistry. As a matter of consequence, our present knowledge on high-valent organotransition metal compound is comparatively shallow, nor do we know much about the chemical relationship and interconvertability of high and low oxidation states within a given class of compounds. In this article I want to point out some ostensibly challenging perspectives of future organometallic research by describing a novel class of high oxidation state organorhenium compounds as well as by speculating on possible generalizations for other transition metals.
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
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