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  • 1
    ISSN: 1434-1948
    Keywords: Iron(III) ; Peroxo Complexes ; Kinetics ; Hydrogen Peroxide ; Catalase ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new diiron complex [Fe2(tbpo){O2As(CH3)2}(CH3O)(CH3OH)](ClO4)3 · 5 CH3OH · 2 H2O (1) containing a (μ-alkoxo)(μ-dimethylarsinato)diiron(III) core was synthesized using the heptadentate ligand N,N,N′,N′-Tetrakis(2-benzimidazolylmethyl)-1,3-diamino-2-propanol (Htbpo). The complex was characterized structurally by X-ray crystallography. 1reproduces the coordination mode and the stoichiometry of the proposed purple acid phosphatase-arsenate inhibitor complex. More importantly, 1 is a good functional model for the activation of small molecules, since the solvent molecule in the coordination sphere of each iron ion can be substituted very easily by a small substrate molecule. This is confirmed by the comparatively high pH-dependent catalase-like activity of 1. In order to study the influence of the cacodylate bridge on the formation of the metastable adduct with hydrogen peroxide, the analogous hydroxo-bridged complex [Fe2(tbpo)(OH)(NO3)2](NO3)2 · CH3OH · 2 H2O (2) was employed. The reactions of 1and 2 with H2O2 were studied as a function of [H2O2], pH, temperature, and pressure, and the kinetic results including the activation parameters are reported. In the case of compound 2 the reaction proceeds in one step, and the observed first order rate constant, kobs, shows a linear dependence on the hydrogen peroxide concentration with a zero intercept. For complex 1 the kinetic traces could be fitted to two exponential functions. One of the observed pseudo-first-order rate constants, kobs1, exhibits a linear dependence on the hydrogen peroxide concentration with a zero intercept, whereas the other rate constant, kobs2, was independent of the hydrogen peroxide concentration. A mechanistic interpretation is presented.Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2005/1999/99068_s.pdf or from the author.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0947-6539
    Keywords: heterocycles ; insertion reactions ; phosphaalkynes ; phosphorus ylides ; triphosphetenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hitherto unknown 1,2,3-triphosphetenes RC=P—PCF3—PCF3 (3a-d) are formed as main products in reactions of phosphaalkynes R—C≡P [R = iPr2N (1a), tBu (1b), Me2EtC (1c), 1-methylcyclohexyl (1d)] with the cyclotetraphosphane (PCF3)4 (2). According to NMR results the CF3 groups in 3a-d have a trans disposition; an X-ray diffraction study of 3a confirms this structure. The P—P bond lengths in 3a are equal [2.201 (2) and 2.204 (2) Å] and correspond to single bonds. A considerable shortening is observed for the sp2-C-N bond (1.336 Å) which, together with the elongation of the P=C bond (1.746 Å), indicates effective π donation of the lone pair on nitrogen. Surprisingly, 3a can be prepared in quantitative yields by reaction of the PP ylide Me3P=PCF3 (6) with 1 a (molar ratio: 2:1). In contrast, the corresponding reactions of 6 with the alkyl-substituted phosphaalkynes 1b-d lead to the novel phosphorus ylides Me3P=C(R)—P—PCF3—PCF3PCF3 [R = tBu (10a), Me2EtC (10b), 1-methylcyclohexyl (10c)] in good yields. In their molecular groundstate structures, determined by X-ray diffraction, the lone pair on the phosphano P atom prefers the syn position with respect to the ylidic P=C bond. An unusual lengthening of the sp2-C-C bond [1.553 (4) (10a), 1.543 (6) (10b), 1.551 (4) Å (10c)] to values typical for sp3-C/sp3-C distances is observed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 3 (1997), S. 1232-1237 
    ISSN: 0947-6539
    Keywords: antimony ; heteropolyanions ; polyoxometalates ; synthesis design ; tungsten ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Proceeding from the α-B-SbW9O33 fragment 1, various novel large heteropolyanions ([Na2Sb8W36O132(H2O)4]22- (2), [Sb2W22O74(OH)2]12- (3) and [Sb2W20M2O70(H2O)6](14-2n)- (4); Mn+ = Fe3+, Co2+, Mn2+, Ni2+) have been obtained in crystalline form by systematic synthesis. Their unexpected structures have been studied by X-ray diffraction: 2, 3 and 4 contain β-SbW9 units connected to each other by Sb3+ ions, WO2/WO2OH groups, and WO2/Mn+ (H2O)3 groups, respectively. Structural details and especially the systematic synthesis strategy for the formation of these interesting polytungstates are discussed in order to explain the unusual behaviour of 1 in aqueous solution under different reaction conditions.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 109 (1997), S. 1995-1996 
    ISSN: 0044-8249
    Keywords: Bor ; Cluster ; Festkörperstrukturen ; Festphasensynthesen ; Selen ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 108 (1996), S. 2158-2191 
    ISSN: 0044-8249
    Keywords: Enzymkatalyse ; Metallohydrolasen ; Katalyse ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sowohl bei enzymatischen als auch bei nichtenzymatischen Katalysen sind zahlreiche Untersuchungen durchgeführt worden, um zu verstehen, wie Metallionen - besonders Zinkionen - die Hydrolyse von Phosphorsäureester- und Amidbindungen unterstützen. Hydrolasen mit einem Metallion im aktiven Zentrum, sogenannte mononucleare Metallohydrolasen, z. B. die Carboxypeptidase A oder Thermolysin, zählen zu den ersten Enzymen, deren Strukturen röntgenographisch aufgeklärt werden konnten. In den letzten Jahren wurden zunehmend mehr Metalloenzyme charakterisiert, in denen zwei oder mehrere benachbarte Metallionen die Katalyse von Phosphoryl- (ROPO3 + R′OH → R′OPO3 + ROH; im Fall der Phosphatasereaktion ist R′-OH ein Wassermolekül) und von Carbonyltransferreaktionen unterstützen, z. B. in Peptidasen und anderen Amidasen. Diese dinuclearen Metalloenzyme katalysieren enorm viele Reaktionen dieser Art: die hydrolytische Spaltung von Phosphorsäuremono-, di- und triesterbindungen, von Phosphorsäureanhydridbindungen sowie die Spaltung von Peptidbindungen oder Harnstoff. Auch die Bildung der Phosphodiesterbindung in RNA und DNA wird von Polymerasen über einen Zwei-Metallionen-Mechanismus katalysiert. Erstaunlich vielfältig sind auch die Strukturen der aktiven Zentren dieser di- oder trinuclearen Metalloenzyme, selbst für Enzyme, die sehr ähnliche Reaktionen katalysieren. Die Strukturbestimmung des aktiven und inaktivierten Enzyms mit gebundenem Substrat oder Produkt, einem stabilen Intermediat oder einem Analogon einer sich im Verlauf der Reaktion bildenden Zwischenstufe ist eine leistungsstarke Methode zur Aufklärung der mechanistischen Details der Enzymkatalyse. Strukturbestimmungen sind für viele der in diesem Artikel beschriebenen Metalloenzyme durchgeführt worden und liefern zusammen mit anderen biochemischen Untersuchungen einen immer besseren Einblick in die Fragestellung, wie die zwei (oder mehr) Metallionen zusammenwirken, um die Reaktionen effizient zu katalysieren.
    Additional Material: 34 Ill.
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  • 6
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0044-2313
    Keywords: Zinc complex ; iron complex ; tripodal ligand ; benzimidazole ; imidazole ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Tripodliganden: Darstellung verzerrter Koordinationspolyeder in biomimetischen Metallkomplexen. Kristallstrukturen von [Zn(SCN)(ntb)](SCN) · iPrpOH und [Fe(acac)(ntb)](ClO4)2 · 2 CH2Cl2 · iPrpOH, ntb = N-Tris(2-benzimidazolylmethyl)aminDer Tripodligand N-Tris(2-benzimidazolylmethyl)amin (ntb) wurde zur Synthese eines Zink(II)- und eines Eisen(III)-Komplexes, [Zn(SCN)(ntb)](SCN) · iPrpOH (1) und [Fe(acac)(ntb)](ClO4)2 · 2 CH2Cl2 · iPrpOH (2), eingesetzt. Der Zinkkomplex hat eine stark verzerrte trigonal-bipyramidale Koordinationssphäre. Die koordinierenden Atome sind ein Amin-N, drei Benzimidazol-N und ein SCN--N-Atom. Auffällig hier ist der 2.539(6)Å große Zn—Namin-Bindungsabstand. Das Koordinationspolyeder des Eisenkomplexes ist weniger stark verzerrt als das in 1 und wird von einem Amin- und drei Benzimidazol-Stickstoffatomen des Liganden sowie zwei Sauerstoffatomen des Acetylacetonats gebildet. Die Fe—O-Bindungslängen zeigen eine Differenz von ca. 0.1 Å, die wie die ungewöhnlich lange Zn—N-Bindung durch einen Trans-Effekt verursacht wird. 1 kristallisiert triklin in der Raumgruppe P1 mit: a = 9.530(1), b = 13.402(1), c = 13.578(2)Å, α = 98.83(1), β = 95.19(1), γ = 101.21(1)°, Z = 2; 2 ist ebenfalls triklin, P1, mit: a = 9.875(6), b = 12.929(10), c = 18.635(15)Å, α = 94.95(8), β = 101.01(6), γ = 111.09(4)°, Z = 2.
    Notes: The tripodal ligand N-tris(2-benzimidazolylmethyl)-amine (ntb) was used for the preparation of zinc(II) and iron(III) complexes, [Zn(SCN)(ntb)](SCN) · iPrpOH (1) and [Fe(acac)(ntb)](ClO4)2 · 2CH2Cl2 · iPrpOH (2). 1 has a highly distorted trigonal-bipyramidal ZnN5 coordination geometry. The donor atoms are nitrogens of one amine, three benzimidazoles and one SCN-. A striking feature of the complex is the length of the Zn—Namine bond of 2.539(6)Å. The octahedral N4O2 coordination sphere of the iron in 2 is less distorted than that of the zinc in 1. The metal is surrounded by an amine and three benzimidazole nitrogens of the ligand and two oxygens of the bidentate acetylacetonate co-ligand. The Fe—O bond lengths differ by about 0.1 Å. As for the unusual long Zn—N bond in 1 this is a result of a trans effect. 1 crystallizes in the space group P1 with: a = 9.530(1)Å, b = 13.402(1)Å, c = 13.578(2)Å, α = 98.83(1), β = 95.19(1), γ = 101.21(1)°, Z = 2; 2 is also triclinic, space group P1, with: a = 9.875(6)Å, b = 12.929(10)Å, c = 18.635(15)Å, α = 94.95(8)°, β = 101.01(6)°, γ = 111.09(4)°, Z = 2.
    Additional Material: 4 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 36 (1997), S. 1903-1904 
    ISSN: 0570-0833
    Keywords: boron ; clusters ; selenium ; solid-phase synthesis ; solid-state structures ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 0570-0833
    Keywords: complexes with oxygen ligands ; enzyme models ; iron compounds ; oxidations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 35 (1996), S. 2024-2055 
    ISSN: 0570-0833
    Keywords: catalysis ; enzymatic catalysis ; metallohydrolases ; Catalysis ; Enzyme catalysis ; Metalloenzymes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Numerous studies, both in enzymatic and nonenzymatic catalysis, have been undertaken to understand the way by which metal ions, especially zinc ions, promote the hydrolysis of phosphate ester and amide bonds. Hydrolases containing one metal ion in the active site, termed mononuclear metallohydrolases, such as carboxypeptidase. A and thermolysin were among the first enzymes to have their structures unraveled by X-ray crystallography. In recent years an increasing number of metalloenzymes have been identified that use two or more adjacent metal ions in the catalysis of phosphoryl-transfer reactions (R-OPO3 + R′-OH → R′-OPO3 + R-OH; in the case of the phosphatase reaction R′-OH is a water molecule) and carbonyl-transfer reactions, for example, in peptidases or other amidases. These dinuclear metalloenzymes catalyze a great variety of these reactions, including hydrolytic cleavage of phosphomono-, -di- and -triester bonds, phosphoanhydride bonds as well as of peptide bonds or urea. In addition, the formation of the phosphodiester bond of RNA and DNA by polymerases is catalyzed by a two-metal ion mechanism. A remarkable diversity is also seen in the structures of the active sites of these di- and trinuclear metalloenzymes, even for enzymes that catalyze very similar reactions. The determination of the structure of a substrate, product, stable intermediate, or a reaction coordinate analogue compound bound to an active or inactivated enzyme is a powerful approach to investigate mechanistic details of enzyme action. Such studies have been applied to several of the metalloenzymes reviewed in this article; together with many other biochemical studies they provide a growing body of information on how the two (or more) metal ions cooperate to achieve efficient catalysis.
    Additional Material: 34 Ill.
    Type of Medium: Electronic Resource
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