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  • 1
    Electronic Resource
    Electronic Resource
    Trifluoromethyl phosphaalkenes of the type F3CP=C(OR)NR2: Synthesis, spectroscopic investigations, and ligand properties [1]Dedicated to Professor Marianne Baudler on the occasion of her seventieth birthday. (1991)
    New York, NY [u.a.] : Wiley-Blackwell
    Heteroatom Chemistry 2 (1991), S. 385-394 
    Details
    ISSN: 1042-7163
    Keywords: Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The one-pot reaction of the alcohol adducts F3CP(H)CF2OR of perfluoro-2-phosphapropene with secondary amines in a 1:3 molar ratio affords the stable phosphaalkenes F3CP=C(OR)NR2 (R = Me, Et) 1-4 in yields of 58%. NMR and He(I) PE spectroscopic investigations show that the lone pair electrons on nitrogen and oxygen participate in n/π conjugation. In contrast to typical low-coordinated double bonds the new derivatives do not react with alcohols, amines, and 1,3-dienes. The derivatives are more closely related to the phosphaalkenes F3=C(F)NR2 than to perfluoro-2-phosphapropene. The reaction of F3=C(OEt)NMe2 (3) with Cr(CO)5THF yields the η1(P) complex Cr(CO)5[F3CP=C(OEt)NMe2] (7) with an unusually long sp2 PC bond (1.809 Å).
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hc.520020306
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  • 2
    Electronic Resource
    Electronic Resource
    Reactions of iPr2N—C≡P with methylating agents: Formation of the diamino-2-phosphaallylic cation ⊕Dedicated to Prof. Reinhard Schmutzler on the occasion of his sixtieth birthday. Part 39 of the series Reactive E = C (p-p)π-Systems, Part 38; see Ref. [1]. (1994)
    New York, NY [u.a.] : Wiley-Blackwell
    Heteroatom Chemistry 5 (1994), S. 337-341 
    Details
    ISSN: 1042-7163
    Keywords: Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of di(isopropyl)aminophosphaethyne 1 with iodomethane or the methyl ester of trifluormethylsulfonic acid (methyl triflate) yields the ionic 1λ3, 3λ3-diphosphetene derivatives + X- (2a: X = I; 2b: X = CF3SO3). On the basis of NMR spectroscopic and X-ray diffraction studies, the cation can be described as a combination of an amino-2-phosphaallylic cation and its methylated derivative.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hc.520050404
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  • 3
    Electronic Resource
    Electronic Resource
    New Strategies for the Generation of Large Heteropolymetalate Clusters: The β-B-SbW9 Fragment as a Multifunctional Unit (1997)
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 3 (1997), S. 1232-1237 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chem.19970030810
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  • 4
    Electronic Resource
    Electronic Resource
    Structural and Functional Investigations on Diiron Complexes: Catalase-Like Activity and Mechanistic Studies on the Formation of (μ-Peroxo)diiron(III) Adducts (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1537-1543 
    Details
    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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  • 5
    Electronic Resource
    Electronic Resource
    Trigonal planar koordinierter Schwefel(VI): Die Kristall- und Molekülstrukturen von (R3SiN)3S und (R3CN)3S (R=CH3) bei -130°C (1979)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 1751-1755 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Planar Threefold Coordination of Sulfur(VI): Crystal and Molecular Structures of (R3SiN)3S and (R3CN)3S (R=CH3) at -130°CThe crystal structures of the title compounds were determined from single crystal X-ray data (measured at -130°C) and refined to unweighted R-values of 0.034 for (R3SiN)3S (1) and 0.047 for (R3CN)3S(2). 2 crystallizes in the triclinic space group P1 and 1 in the hexagonal space group P63/m. Both structures exhibit a planar threefold nitrogen coordination of the sulfur but the large coefficients of the temperature factors perpendicular to the SN3 planes in 1 and 2 might indicate a disorder due to small deviations from planarity. The S—N bond lengths were found to be 150.4 (1) and 151.5 pm (2, mean).
    Notes: Die Strukturen der Titelverbindungen wurden aus Diffraktometer-Einkristalldaten (gemessen bei -130°C) bestimmt und zu ungewichteten R-Werten von 0.034 für (R3SiN)3S )(1) und 0.047 für (R3CN)3S (2)verfeinert. 2 kristallisiert triklin, P1. Und 1 hexagonal, P63/m. In beiden Strukturen wird eine trigonal planare Koordination des zentralen Schwefelatoms beobachtet, doch deuten die relativ großen Koeffizienten der anisotropen Temperaturfaktoren senkrecht zu den SN3-Ebenen in 1 und 2 auf eine Fehlordnung als Folge geringer Abweichungen von der Planarität in den einzelnen Molekülen hin. Die S—N-Abstände betragen 150.4 pm (1) und 151.5 pm (2, Mittelwert).
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19791120525
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  • 6
    Electronic Resource
    Electronic Resource
    Kristall- und Molekülstrukturen des S3N2+-Radikalkations in S3N2+SO3CF3- · 1/2 CH3CN und von S3N2(NSO2F) (1980)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 113 (1980), S. 226-232 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal and Molecular Structures of the S3N2+ Radical Cation in S3N2+SO3CF3- · 1/2 CH3CN and of S3N2(NSO2F)The molecular and crystal structures of S3N2+SO3CF3- · 1/2 CH3CN (1) and S3N2NSO2F (2) were determined from single crystal X-ray diffraction data. The S3N2+ radical cation in 1 is planar, two cations being connected through weak S—S bonding interactions to form dimers with a chair configuration. The S3N2 ring of 2, in which the NSO2F group is covalently bonded to one of the S atoms of the S — S group, is not planar; the S — S bond is weaker than in 1.
    Notes: Die Röntgenstrukturanalysen von S3N2+SO3CF3- - 1/2 CH3CN (1) und S3N2NSO2F (2) zeigen in 1 ein planares S3N2+-Radikalkation, wobei zwei Kationen über schwache S-S-Wechselwirkungen zu sesselförmigen Dimeren assoziiert sind. Der an einem S-Atom der S — S-Gruppe substituierte S3N2-Ring in 2 ist nicht planar; die S — S-Bindung ist schwächer als in 1.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19801130123
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  • 7
    Electronic Resource
    Electronic Resource
    Schwingungsspektroskopische Untersuchungen anorganischer Festkörper. XVIII. Die IR-Schwingungsspektren des CS42--Ions und der polymeren Kohlenstoff - Schwefel-Verbindungen (CS2+x)n HMO-Rechnung für das CS42--Ion (1966)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 347 (1966), S. 261-268 
    Details
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The infrared absorption frequencies of the CS42- ion are reported and interpreted in terms of a nontetrahedral structure. The IR spectra of the polymeric compounds (CS2+x)n with x = 0-3 are summarised and discussed. Assignments for the observed absorption frequencies of all compounds are given. Using the HÜCKEL MO method, approximate π bond orders and π electron densities are calculated for the CS42--ion.
    Notes: Das IR-Spektrum des CS42--Ion wird angegeben und daraus eine nichttetraedrische Struktur abgeleitet. Weiterhin wird über die Infrarotspektren der polymeren Verbindungen (CS2+x)n zusammenfassend berichtet. Die beobachteten Schwingungsfrequenzen des CS42--Ions und der Polymerisate werden nach Gruppenfrequenzen zugeordnet und im Hinblick auf die Bindungsverhältnisse diskutiert. Für das Perthiocarbonation wird eine einfache HMO-Rechnung durchgeführt und mit einer entsprechenden Rechnung für das CS32--Ion verglichen.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19663470506
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  • 8
    Electronic Resource
    Electronic Resource
    Technetium(VII)-oxid: Ein Übergangsmetalloxid mit Molekülstruktur im festen Zustand (1971)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 380 (1971), S. 146-159 
    Details
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Tc2O7 crystallizes in the orthorhombic space group Pbca with a = 13.756, b = 7.439, c = 5.617 Å, Z = 4. The single crystal structure analysis shows the crystals to contain isolated centrosymmetric Tc2O7 molecules with a linear central Tc—O—Tc bridge and with, tetrahedral coordination of the Tc atoms. Tc—O bond lengths: 1.840 (bridge), 1.658, 1.684 and 1.706 Å. The structure is more closely related to CrO3, RuO4 and OsO4 than to Re2O7.Structural properties of the d° transition metal oxides are briefly discussed.
    Notes: Tc2O7 kristallisiert orthorhombisch mit a = 13,756, b = 7,439, c = 5,617 Å, Z = 4 in der Raumgruppe Pbca. Die vollständige Röntgenstrukturanalyse zeigt, daß im Kristall zentrosymmetrische Tc2O7-Molekeln mit tetraedrischer Koordination des Metalls und linearer Tc—O—Te-Brücke vorliegen. Tc—O-Bindungsabstände: 1,840 (Brücke), 1,658, 1,684 und 1,706 Å.Damit sind Struktur und Koordinationsverhältnisse der Kettenstruktur des CrO3 und den Molekülstrukturen von RuO4 und OsO4 ähnlicher als der polymeren Schichtstruktur des Re2O7.Struktureigensehaften von d°-Übergangsmetalloxiden werden kurz im Zusammenhang diskutiert.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19713800205
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  • 9
    Electronic Resource
    Electronic Resource
    Dimere Halogenotellurate(IV): Darstellung und Kristallstruktur von [(C6H5)4P] 2Te2Br10 (1980)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 463 (1980), S. 56-64 
    Details
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Dimeric Halogenotellurates(IV): Preparation and Crystal Structure of [(C6H5)4P] 2Te2Br10Similar to the isotypic Te4Cl16, the cubane-like Te4Br16 can be fragmented to oligomeric and monomeric halogenotellurates(IV). [(C6H5)4P]2Te2Br10 is formed by reaction of TeBr4 with (C6H5)4PBr in benzene/acetonitrile solution. The X-ray structural analysis of the compound (a = 10.744, b = 11.787, c = 12.179 Å, α = 71.47°, β = 85.64°, γ = 72.28°, space group P1, Z = 1) shows dimeric Te2Br102- ions to be present, consisting of edge-sharing distorted TeBr6 octahedra. The Te—Br bond lengths are 2.530(2).2.698(2) Å (mean value 2.614 Å) for the terminal, 2.876(2) and 3.000(2) Å for the bridge bonds. The stereochemical activity of the inert pairs at the Te atoms is only weak. The infrared and Raman spectra of the Te2Br102- ion are reported.
    Notes: Wie das isotype Te4Cl16 kann auch das cubanartige Te4Br16 zu oligomeren und monomeren Halogenotelluraten(IV) abgebaut werden. [(C6H5)4P]2Te2Br10 entsteht bei der Reaktion von TeBr4 mit (C6H5)4PBr in Benzol/Acetonitril. Die Röntgenstrukturanalyse der Verbindung (a = 10,744, b = 11,787, c = 12,179 Å, α = 71,47°, β = 85,64°, γ = 72,28°, Raumgruppe P1, Z = 1) zeigt, daß ein dimeres, aus kantenverknüpften, verzerrten TeBr6-Oktaedern bestehendes Te2Br102--Ion vorliegt. Die Te—Br-Bindungslängen betragen 2,530(2).2,698(2) Å (Mittelwert 2,614 Å) für die endständigen, 2,876(2) und 3,000(2) Å (M.2,938 Å) für die Brückenbindungen. Die stereochemische Aktivität der inerten Elektronenpaare am Te ist nur gering. Über die IR- und Raman-Spektren des Te2Br Br102--Ions wird berichtet.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19804630107
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  • 10
    Electronic Resource
    Electronic Resource
    Neue PdxAly-Phasen und die Verbindung Pd5AII2 (1980)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 462 (1980), S. 49-56 
    Details
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New PdxAly Phases and the Compound Pd5AII2The new phases Pd2.4-2.9Al, Pd2.99-3.3Al, and Pd3.8-4.15Al were prepared by synthesis from molten mixtures and subsequent annealing at 600°C, or by reaction in the presence of iodine at 600°C, and were identified by X-ray powder diagrams. In the iodine-containing systems, the same phases resulted from the relation between composition of the gas phase and the structure of the solid reaction component.The existence of Pd5Al3 was confirmed.The new compound Pd5AlI2, the crystal structure of which was determined from a single crystal X-ray analysis, has a tetragonal layer structure with a = 405.2 and c = 1955.9 pm, space group I4/mmm. Iodine layers alternate with ordered Pd/Al slabs. The compound is a metallic conductor with highly preferred conductivity parallel to the layers.
    Notes: Durch Schmelzsynthese und Temperung bei 600°C sowie durch Synthese in Gegenwart von Iod bei 600°C wurden rötgenographisch die neuen Phasen Pd2,4-2,9Al, Pd2,99-3,3Al und Pd3,8-4,15Al gefunden. Die gleichen Phasen ergaben sich im iodhaltigen System aus dem Zusammenhang von Gasphasenzusammensetzung und Bodenkörperstruktur.Die. Existenz von Pd5Al3 wurde bestätigt.Die neue Verbindung Pd5AlI2, deren Kristallstruktur aus Einkristall-Röntgendaten bestimmt wurde, besitzt ein tetragonales Schichtgitter mit a = 405,2 und c = 1955,9 pm, Raumgruppe I4/mmm, in dem Iodschichten und Pd/Al-Schichten miteinander abwechseln. Die Verbindung ist ein metallischer Leiter mit stark bevorzugter Leitfähigkeit in Richtung der Schichten.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19804620106
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