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  • 1
    ISSN: 1573-6881
    Keywords: Terminal oxidase ; redox coupling ; electrochemical gradient ; electron transport ; energy transduction ; proton translocation ; crystal structure ; site-directed mutagenesis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Physics
    Notes: Abstract One of the challenging features of energy-transducing terminal oxidases, like the aa 3 cytochrome c oxidase of Paracoccus denitrificans, is the translocation of protons across the cytoplasmic membrane, which is coupled to the transfer of electrons to oxygen. As a prerequisite for a more advanced examination of the enzymatic properties, several amino acid residues, selected on the basis of recent three-dimensional structure determinations, were exchanged in subunit I of the Paracoccus enzyme by site-directed mutagenesis. The properties of the mutated oxidases were analyzed by different methods to elucidate whether they are involved in the coupled and coordinated transfer of protons via two different pathways either to the site of oxygen reduction or through the enzyme from the cytoplasm to the periplasmic side.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 685-688 
    ISSN: 0044-2313
    Keywords: Copper antimony selenide ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Crystal Structure of Cu3SbSe3The hitherto unknown crystal structure of Cu3SbSe3 has been determined from single crystals. The compound crystallizes in the orthorhombic system, space group Pnma (No. 62), with a = 7.9865(8), b = 10.6138(9) and c = 6.8372(7) Å, V = 579.6(1) Å3, Z = 4. Most remarkable feature of the structure are groups of three cis-edge-sharing tetrahedra [Cu3Se8] which are interlinked to a threedimensional arrangement by SbSe3-units. In contrast to Cu3SbS3 in the temperature range from -180 to 25°C no hints for a phase transition could be detected by means of X-ray- and thermoanalytical methods.
    Notes: Die bisher unbekannte Kristallstruktur von Cu3SbSe3 wurde aus Einkristalldaten ermittelt. Die Verbindung kristallisiert orthorhombisch, RG Pnma (Nr. 62) mit a = 7,9865(8), b = 10,6138(9) und c = 6,8372(7) Å, V = 579.6(1) Å3, Z = 4. Die Struktur zeichnet sich durch Baugruppen [Cu3Se8] aus drei cis-kantenverknüpften Tetraedern aus, die über ihre Liganden mit SbSe3-Gruppen zu einem dreidimensionalen Netzwerk verknüpft sind. Im Gegensatz zu Cu3SbS3 konnten Hinweise auf eine Phasenumwandlung im Temperaturbereich von -180 bis 25°C weder durch röntgenographische noch durch thermoanalytische Untersuchungen gefunden werden.
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  • 3
    ISSN: 0044-2313
    Keywords: Yttrium complexes ; yttrium tris[bis(trimethylsilyl)amide] ; yttrium tris[bis(trimethylsilyl)methanide] ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Bis(trimethylsilyl)amides and -methanides of Yttrium  -  Molecular Structures of Tris(diethylether-O)lithium-(μ-chloro)-tris[bis(trimethylsilyl)methyl]yttriate, solvent-free Yttrium Tris[bis(trimethylsilyl)amide] as well as the Bis(benzonitrile) ComplexThe reaction of yttrium(III) chloride with the three-fold molar amount of LiE(SiMe3)2 (E = N, CH) yields the corresponding yttrium derivatives. Yttrium tris-[bis(trimethylsilyl)amide] crystallizes in the space group P31c with a = 1 636,3(2), c = 849,3(2) pm, Z = 2. The yttrium atom is surrounded trigonal pyramidal by three nitrogen atoms with Y—N-bond lengths of 222 pm. Benzene molecules are incorporated parallel to the c-axes. The compound with E = CH crystallizes as a (Et2O)3LiCl-adduct in the monoclinic space group P21/n with a = 1 111,8(2), b = 1 865,2(6), c = 2 598,3(9) pm, β = 97,41(3)° and Z = 4. The reaction of yttrium tris[bis(trimethylsilyl)amide] with benzonitrile yields the bis(benzonitrile) complex, which crystallizes in the triclinic space group P1 with a = 1 173,7(2), b = 1 210,3(2), c = 1 912,4(3) pm, α = 94,37(1), β = 103,39(1), γ = 117,24(1)° and Z = 2. The amido ligands are in equatorial, the benzonitrile molecules in axial positions.
    Notes: Die Reaktion von Yttrium(III)-chlorid mit der dreifachen molaren Menge LiE(SiMe3)2 (E = N, CH) ergibt die entsprechenden Yttrium-Derivate. Yttrium-tris[bis(trimethylsilyl)amid] kristallisiert in der Raumgruppe P31c mit a = 1 636,3(2), c = 849,3(2) pm, Z = 2. Das Yttriumatom ist trigonal pyramidal koordiniert mit Y—N-Bindungslängen von 222 pm. Entlang der c-Achse sind Benzolmoleküle eingeschlossen. Die Verbindung mit E = CH kristallisiert als (Et2O)3LiCl-Addukt in der monoklinen Raumgruppe P21/n mit a = 1 111,8(2), b = 1 865,2(6), c = 2598,3(9) pm, β = 97,41(3)° und Z = 4. Die Umsetzung von Yttrium-tris[bis(trimethylsilyl)amid] mit Benzonitril ergibt einen Bis(benzonitril)-Komplex, der in der triklinen Raumgruppe P1 mit a = 1173,7(2), b = 1210,3(2), c = 1912,4(3) pm, α = 94,37(1), β = 103,39(1), γ = 117,24(1)° und Z = 2 kristallisiert. Die Amido-Liganden sind äquatorial, die Benzonitril-Moleküle axial koordiniert.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 8-15 
    ISSN: 0044-2313
    Keywords: P3B and P4B ring systems ; NMR data ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Structure Analysis of (i-Pr)2NB(t-BuP)3 and (i-Pr)2NB(t-BuP)4The diphosphide K(t-Bu)P-(t-BuP)2-P(t-Bu)K obtained by the cleavage reaction of the 3-membered ring system (i-Pr)2BN(t-BuP)2 with potassium reacts with t-BuPCl2 at -78°C under ring expansion to form the P3B ring system (i-Pr)2NB(t-BuP)3 - 1,2,3-tri-t-butyl-tri-phospha-4-diisopropyl-aminoboretane (1). - The 5-membered P4B ring system (i-Pr)2NB(t-BuP)4 - 1,2,3,4-tetra-t-butyl-tetraphospha-5-diisopropylaminoborolidine, (2) - is formed from K(t-Bu)P—(t-BuP)2—P(t-Bu)K and (i-Pr)2NBCl2 analogous to the above reaction. 1 and 2 could be obtained in a pure form and characterized NMR spectroscopically and by X-ray structure analysis. 1 shows at 200 K two conformation isomers; for 2 31P-10,11B-isotopic shifts could be identified.
    Notes: Das bei der Spaltung des Dreiringes (i-Pr)2BN(t-BuP)2 mit Kalium gebildete Diphosphid K(t-Bu)P—BN(i-Pr)2—P(t-Bu)K reagiert bei -78°C mit t-BuPCl2 unter Ringerweiterung zu (i-Pr)2NB(t-BuP)3-1,2,3-Tri-t-butyl-triphospha-diisopropyl-aminoboretan, (1) - mit einem P3B-Ringgerüst. In analoger Weise entsteht bei der Reaktion zwischen K(t-Bu)P—(t-BuP) - (t-BuP)2—P(t-Bu)K und (i-Pr)2NBCl2 das P4B-Ringsystem (i-Pr)2NB(t-BuP)4 - 1,2,3,4-Tetra-t-butyl-tetraphospha-5-diiso-propylaminoborolidin, (2) -, 1 und 2 konnten in reiner Form isoliert, NMR-spektroskopisch und durch Röntgenstrukturanalysen charakterisiert werden. 1 zeigt bei 200 K zwei Konformationsisomere; bei 2 konnten 31P-10,11B-Isotopieverschiebungen nachgewiesen werden.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 1992-1997 
    ISSN: 0044-2313
    Keywords: Copper antimony sulfide ; sulfo salts ; crystal structure ; phase transitions ; Extended Hückel calculations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cu3SbS3: Crystal Structure and PolymorphismThe hitherto unknown crystal structure of β-Cu3SbS3 at room temperature could be determined from a twinned crystal. The compound crystallizes in the monoclinic system, space group P21/c (No. 14), with a = 7.808(1), b = 10.233(2) and c = 13.268(2) Å, β = 90.31(1)°, V = 1 060.1(2) Å3, Z = 8. An Extended-Hückel-Calculation shows weak bonding interactions between copper atoms which are coordinated trigonal planar. At -9°C a first order phase transition occurs and the crystals disintegrate. The low-temperature modification (γ) crystallizes in the orthorhombic system with a = 7.884(2), b = 10.219(2) and c = 6.623(2) Å, V = 533.6(2) Å3 (-100°C). At 121°C a phase transition of higher order is observed. The high-temperature polymorph (α) of Cu3SbS3 is orthorhombic again. From high-temperature precession photographs the space groups Pnma (No. 62) or Pna21 (No. 33) can be derived. The lattice constants at 200°C are a = 7.828(3), b = 10.276(4) and c = 6.604(3) Å, V = 531.2(2) Å3.
    Notes: Die bisher unbekannte Kristallstruktur von β-Cu3SbS3 bei Zimmertemperatur wurde anhand eines verzwillingten Kristalls ermittelt. Die Verbindung kristallisiert monoklin, RG P21/c (Nr. 14) mit a = 7,808(1), b = 10,233(2) und c = 13,268(2) Å, β = 90,31(1)°, V = 1 060,1(2) Å3, Z = 8. Eine Extended-Hückel-Rechnung ergibt schwach bindende Wechselwirkungen zwischen den trigonal-planar koordinierten Kupferatomen. Bei -9°C erfolgt eine reversible Phasenumwandlung 1. Ordnung, bei der die Kristalle zerfallen. Die Tieftemperaturmodifikation (γ) kristallisiert orthorhombisch mit a = 7,884(2), b = 10,219(2) und c = 6,623(2) Å, V = 533,6(2) Å3 (-100°C). Beim Aufheizen beobachtet man bei 121°C eine Phasenumwandlung höherer Ordnung. Die Hochtemperaturmodifikation (α) von Cu3SbS3 kristallisiert ebenfalls orthorhombisch. Aus Hochtemperatur-Präzessionsaufnahmen ergibt sich Pnma (Nr. 62) oder Pna21 (Nr. 33) als mögliche Raumgruppe. Die Gitterkonstanten bei 200°C sind nach Guinier-Aufnahmen a = 7,828(3), b = 10,276(4) und c = 6,604(3) Å, V = 531,2(2) Å3.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 969-974 
    ISSN: 0044-2313
    Keywords: Copper(I) selenium tellurium halides ; chalcogen ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: CuSeTeCl, CuSeTeBr, and CuSeTeI: Compounds with ordered ∞1[SeTe] ScrewsThe hitherto unknown copper(I) chalcogen halides CuSeTeCl, CuSeTeBr and CuSeTeI have been prepared and their crystal structures were determined. The compounds of general composition CuSeTeX crystallize in the monoclinic system, space group P21/n (No. 14), Z = 4, a = 7.9796(9), b = 4.7645(8), c = 10.843(3) Å, β = 104.12(1)°, V = 399.8(1) Å3 (X = Cl), a = 8.155(3), b = 4.765(2), c = 11.286(4) Å, β = 104.21(3)°, V = 425.1(3) Å3 (X = Br) and a = 8.4370(9) b = 4.7652(5), c = 11.996(2) Å, β = 103.178(9)°, V = 469.6(1) Å3 (X = I). The crystal structures show infinite onedimensional screws YY′ of chalcogen atoms, with Y = Se and Y′ = Te alternately. The coordinations of Se and Te in these compounds are quite different.
    Notes: Die bisher unbekannten Kupfer(I)-chalkogenhalogenide CuSeTeCl, CuSeTeBr und CuSeTeI wurden erstmals erhalten und ihre Kristallstrukturen bestimmt. Sie kristallisieren monoklin, RG P21/n (Nr. 14), Z = 4, mit a = 7,9796(9), b = 4,7645(8) und c = 10,843(3) Å, β = 104,12(1)°, V = 399,8(1) Å3 (X = Cl), a = 8,155(3), b = 4,765(2) und c = 11,286(4) Å, β = 104,21(3)°, V = 425,1(3) Å3 (X = Br) sowie a = 8,4370(9), b = 4,7652(5) und c = 11,996(2) Å, β = 103,178(9)°, V = 469,6(1) Å3 (X = I). In den Kristallstrukturen liegen eindimensional unendliche Schrauben YY′ vor, mit alternierend Y = Se und Y′ = Te. Die Umgebungen von Se und Te sind deutlich verschieden.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 622 (1996), S. 853-857 
    ISSN: 0044-2313
    Keywords: Copper(I) sulfur tellurium halides ; chalcogen ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: CuClS0.94Te1.06 and CuBrS0.92Te1.08, Two New Copper(I) Chalcogen Halides Containing Neutral ∞1[STe] ScrewsCuClS0.94Te1.06 and CuBrS0.92Te1.08 are two new, isotypic compounds of general composition CuXYY′ (X = halide, Y, Y′ = chalcogen) with a mixed chalcogen substructure. They crystallize in the monoclinic system, space group P21/n (No. 14), a = 7.878(2), b = 4.727(1), c = 10.759(2) Å, β = 103.97(2)°, V = 388.8(2) Å3 (CuClS0.94Te1.06) and a = 8.043(3), b = 4.746(2), c = 11.240(4) Å, β = 103.46(3)°, V = 417.3(3) Å3 (CuBrS0.92Te1.08), both with Z = 4. The crystal structures are dominated by ordered ∞1[STe±0]-screws. From a crystal chemical point of view the sulfur and tellurium atoms are significantly different. The melting points are 341 °C (CuClS0.94Te1.06) and 336 °C (CuBrS0.92Te1.08). The compounds CuXYY′ (X = Cl, Br, I; Y, Y′ = S, Se, Te) are compared and discussed.
    Notes: Mit CuClS0.94Te1.06 und CuBrS0.92Te1.08 wurden zwei neue, isotype Verbindungen der Zusammensetzung CuXYY′ (X = Halogenid, Y, Y′ = Chalkogen) mit gemischtem Chalkogenteilgitter erhalten. Sie kristallisieren monoklin, RG P21/n (Nr. 14) mit a = 7,878(2), b = 4,727(1) und c = 10,759(2) Å, β = 103,97(2)°, V = 388,8(2) Å3 (CuClS0.94Te1.06) bzw. a = 8,043(3), b = 4,746(2) und c = 11,240(4) Å, β = 103,46(3)°, V = 417,3(3) Å3 (CuBrS0.92Te1.08), jeweils mit Z = 4. Strukturbestimmendes Merkmal sind die geordneten ∞1[STe±0]-Schrauben. Kristallchemisch sind die Schwefel- und Telluratome deutlich unterschiedlich. Die Schmelzpunkte liegen bei 341 °C (CuClS0.94Te1.06) bzw. 336 °C (CuBrS0.92Te1.08). Die Strukturen von CuXYY′ (X = Cl, Br, I; Y, Y′ = S, Se, Te) werden verglichen und diskutiert.
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  • 8
    ISSN: 0044-2313
    Keywords: Thia- and selena-arachno-undecaborane ; preparation ; spectroscopy ; ab initio/IGLO ; GIAO/NMR method ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thia- and Selena-arachno-undecaborane 6,7-μ-(CH3E)B10H13. Crystal Structure of arachno-6,7-μ-(CH3Se)B10H13. Theoretical Investigations of the Molecular Structures and 11B NMR Shifts of arachno-6,7-μ-(CH3E)B10H13The reaction of B10H14 with (CH3)2S yields with loss of H2 the base adduct 6,9-[(CH3)2S]2B10H12. Although an analogous reaction between B10H14 with disulfanes or diselenanes was expected to produce 6,9 bridged dichalcogen derivatives, (CH3)2S2 failed to react even under reflux conditions. Trisulfane (CH3)2S3 does react, but the pathway is different and leads to (CH3S)B10H13 2 without loss of H2. Unlike of (CH3)2S2, (CH3)2Se2 yields (CH3Se)B10H13, 3. Both 2 and 3 are formed by substitution of a bridging hydrogen and could be obtained in pure form and characterized 11B NMR spectroscopically. A single crystal X-ray structure analysis also was performed on 3 (space group P21/c). The molecular structures of 2 and 3 were optimized at the MP2 level and 11B NMR shifts were computed at the IGLO-SCF, GIAO-SCF and GIAO-B3LYP levels of theory.
    Notes: Bei der Reaktion zwischen B10H14 und (CH3)2S erfolgt unter H2-Abspaltung eine zweifache Adduktbildung, die zu 6,9-[(CH3)2S]2B10H12 führt. Die analoge Umsetzung zwischen B10H14 mit Disulfanen bzw. Diselenanen führte jedoch nicht zu den 6,9-Dichalkogen-verbrückten Derivaten. Bei der Umsetzung mit (CH3)2S2 findet selbst unter Refluxbedingungen keine Reaktion statt, wohl aber mit dem Trisulfan (CH3)2S3. Die Reaktion verläuft aber nicht unter H2-Abspaltung. Vielmehr wird dabei ein Brücken-H-Atom durch eine CH3S-Gruppe substituiert unter Bildung von (CH3S)B10H13 2. Im Gegensatz zu (CH3)2S2 findet aber mit (CH3)2Se2 ebenfalls eine Brücken-H-Substitution statt, wobei (CH3Se)B10H13 3 gebildet wird. 2 und 3 konnten in reiner Form isoliert und 11B-NMR-spektroskopisch charakterisiert werden. Von 3 wurde eine Röntgenstrukturanalyse durchgeführt (Raumgruppe P21/c) und von 2 und 3 die Molekülstrukturen auf MP2-Niveau optimiert sowie 11B-NMR- Verschiebungen mit IGLO-SCF, GIAO-SCF und GIAO-B3LYP berechnet.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 1555-1560 
    ISSN: 0044-2313
    Keywords: Iodocuprate(I) ; [Cu2I4]2- ; tetraphenylphosphonium ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zwei neue Modifikationen von [P(C6H5)4]2[Cu2I4]Bei der Reaktion von granuliertem Kupfer mit Iod und [P(C6H5)4]I in trockenem Aceton unter Stickstoffatmosphäre wurden Einkristalle von zwei neuen Modifikationen von [P(C6H5)4]2[Cu2I4] erhalten. Sie kristallisieren monoklin, Raumgruppe P21/n (Nr. 14), a = 11.550(6), b = 7.236 (2), c = 27.232 (13) Å, β = 98.13(3)°, V = 2253(2) Å3 und Z = 2 ([P(C6H5)4]2[Cu2I4]-C) bzw. Raumgruppe Cc (Nr. 9), a = 17.133(5), b = 15.941(5), c = 18.762(6) Å, β = 114.02(1)°, V = 4681(3) Å3 und Z = 4 ([P(C6H5)4]2[Cu2I4] -D). In diesen Verbindungen liegen dimere di-μ-iodo-diiodocuprat(I)-Einheiten vor, die planar (C) bzw. gewinkelt (D) sind.
    Notes: Single crystals of two new modifications of [P(C6H5)4]2[Cu2I4] were obtained by reaction of granulated copper with iodine and [P(C6H5)4]I in dry acetone under nitrogen atmosphere. They crystallise monoclinically, space group P21/n (No. 14), a = 11.550(6), b = 7.236(2), c = 27.232(13) Å, β = 98.13(3)°, V = 2253(2) Å3, and Z = 2 ([P(C6H5)4]2[Cu2I4]-C), and space group Cc (No. 9), a = 17.133(5), b = 15.941(5), c = 18.762 (6) Å, β = 114.02(1)°, V = 4681(3) Å3, and Z = 4 ([P(C6H5)4]2[Cu2I4]-D), respectively. In these compounds the [CuI2]- anions form dimers di-μ-iodo-diiodocuprate(I), which are either planar (C) or folded (D).
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