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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0009-2940
    Keywords: Chirality ; Chromium complexes ; Helicity ; Configuration (absolute) ; [2.2]Metacyclophanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tricarbonylchromium Complexes of Chiral [2.2]Metacyclophanes: Syntheses, Structures, and Chiroptical PropertiesHPLC-baseline separations of three racemic cyclophanes 3, 4, and 6 on cellulose tris(3,5-dimethylphenyl)carbamate led to their enantiomers with high optical purity. Complexation of (-)-3 and (+)-3 with triamminetricarbonylchromium yielded chiral Cr(CO)3 complexes (-)-(S)P-(3S)M-3a and (+)-(R)P-(3R)M-3a stereoselectively. Derivatisation of the complexes by lithiation and reaction with electrophiles gave new substituted chiral Cr(CO)3 complexes of [2.2]metacyclophanes regio-selectively. X-ray structure analyses of one chiral chromium complex (-)-(R)P-(5S)M-14a and three chiral chromium-free ligands (-)-(S)P-3, (-)-(S)P-4, and (-)-(S)P-6 led to the assignment of the absolute configurations of all chiral compounds discussed here. The influences of substituents on the chiroptical properties are investigated. The helicity of [2.2]metacyclophanes is discussed. For the first time X-ray structure analyses were performed of a bis-Cr(CO)3 complex (9a) as well as of the first chromium complex 10a of a heteraphane. Dethioketalisation of (-)-(S)P-3 with NBS gave (-)-(S)P-18, the absolute chirality of which has been known, under retention of configuration.
    Additional Material: 17 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0009-2940
    Keywords: [2.2]Metacyclophanes ; Chromium tricarbonyl complexes ; Chirality, helical, planar ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Regioselective Substitution of [2.2]Metacyclophanes via Chromium Tricarbonyl ComplexesThe [2.2]metacyclophanes 6, 8, and 9 are regioselectively complexed with triammintricarbonylchromium. The complexes are lithiated with nBuLi/TMEDA at -78°C, and the resulting aryllithium complexes are trapped with electrophiles to give new phanes exhibiting substitution patterns, which are not or more difficult available by other routes. Complex 6a gives 5-substitution almost exclusively, while the chiral complex 8a is substituted in positions 5 and 4 in a ratio of 3:1. Steric effects, caused by the large dithiane group, seem to play a role in both complexation and derivatisation of these substrates. An X-ray crystal structure analysis of the chromium tricarbonyl phane complex 11 is performed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0009-2940
    Keywords: [2.2]Metacyclophanes ; Chromium complexes ; Chirality (helicity, planar chirality) ; Clathrates ; Configuration, absolute ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Regioselective Complexation of [2.2]Metacyclophanes with TriamminetricarbonylchromiumThe new [2.2]phanes 12, 13, 15, and 17 have been prepared. For the preparation of the known phane 16 a new route has been developed which leads to better yields and includes an interesting reduction with Raney nickel of the naphthalene ring of 15 to a tetrahydronaphthalene ring (→17). The phanes react regioselectively with triamminetricarbonylchromium, which results exclusively in the complexation of the sterically less hindered benzene ring. The bis(tricarbonylchromium) complexes of 18 and 17 were available in good yields, when two equivalents of the precursor of the tricarbonylchromium group were used. 18a was lithiated at -78°C, and the lithiated complexes were trapped with either chlorotrimethylsilane or ethyl chloroformate to yield 4- and 5-substituted products in a ratio of 4:5. Ten X-ray structures, including those of six transition metal π complexes, which were investigated and compared under the aspect of steric interactions between the tricarbonylchromium group and the substituent at the arene ring, are discussed. Interestingly, the tricarbonylchromium group shows no noticable effect on the boat-like deformation of the benzene ring in [2.2]metacyclophanes. A new definition of the “angles of helicity” in helical [2.2]phanes is introduced.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 16 (1993), S. 332-337 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The effects of metal exchange between zeolites and alkali metals (Li, Na, K; zeolite Y, ZSM-5, T), alkaline earths (Mg, Ca, Sr, Ba; ZSM-5), transition metals (La, Ce, Cr, Mn, Fe, Co, Ni, Pd, Cu, Zn; ZSM-5) and aluminium (ZSM-5) on the conversion of ethanol were studied. Activities of the catalysts and selectivities for ethene, C3+ olefins, paraffins and arenes strongly depended on the cation, chosen for the modification. Only ethene was formed by alkali exchanged zeolites, the most active being Li-Y. This could be confirmed by a long-term ageing test with Li-Y pellets under semi-industrial conditions. The exchange of ZSM-5 with alkaline earths or transition metals permitted the formation of a wide variety of products, raning from high ethene to high aromatic yields. A correlation between certain product selectivities and electronegativity was only possible in a rough approximation.
    Additional Material: 8 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 17 (1994), S. 179-186 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The conversion of ethanol over H-ZSM-5 was studied as a function of ethanol partial pressure, reaction temperature, weight hourly space velocity and Si/Al ratio. The results obtained were in qualitative agreement with most of those in the literature. Combination with all published results to give a significant regression model was not possible due to the large scatter of the data from various scientific groups. In mechanistic investigations, temperature programmed reaction measurements of ethanol, diethyl ether and ethene were performed. The formation of ethene from ethanol via direct elimination or from diethyl ether as intermediate could be confirmed. In the conversion of ethanol/water mixtures, the product distribution did not change significantly up to a water content of 60 wt%. Then, a pronounced increase of ethene formation and a considerable decrease of the yields of aromatics was observed. When several reaction mixtures from syngas conversion to ethanol were converted over H-ZSM-5, the coking rate depended on the product distribution in the feed. Product mixtures from processes with higher amounts of compounds having an unfavourable C/H ratio led to rapid deactivation of the zeolite.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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