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  • Inorganic Chemistry  (65)
  • Theoretical, Physical and Computational Chemistry  (18)
  • Wiley-Blackwell  (83)
  • American Institute of Physics
  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 69 (1998), S. 629-637 
    ISSN: 0020-7608
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We introduce a new molecular theory beyond the Born-Oppenheimer approximation, where both electrons and nuclei are treated quantum mechanically and equivalently. First, we develop the coupled mean-field theory (CMFT) for both the electronic and nuclear fields. Then, to take into account the dynamic correlation between these particles, we develop a new molecular theory using the generator coordinate method (GCM) based upon the CMFT, which enables us to calculate the molecular eigenstate and eigenvalue directly. Finally, we apply this method to a water molecule and analyze the isotope effect on the vibrational frequency and the particle density.   © 1998 John Wiley & Sons, Inc. Int J Quant Chem 69: 629-637, 1998
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 487 (1982), S. 232-240 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: High Temperature Phosphidation of Iron-Nickel Alloys by Phosphorus VaporA study was undertaken concerning the products and kinetics in the phosphidation of iron-nickel alloys with various ratios of metallic constituents at 700° in phosphorus vapor at 1 atm by a sealed-tube method. X-ray diffraction patterns and an electron microprobe analysis of the products showed that the phosphide-layer structure reaches the expression of NiP2 ∼ Ni6P5/Ni2P, Fe2P/(Fe—Ni alloy). The phosphidations proceeded according to a parabolic rate law for all the compositions of the alloy. A marker experiment indicated that the diffusing species was not phosphorus but metals. The rate constant decreased with an increase in the content of iron in the alloy.
    Notes: Reaktionsprodukte und Kinetik bei der Phosphidierung von Eisen-Nickellegierungen verschiedener Zusammensetzung bei 700° in Phosphordampf (1 atm) im geschlossenen Quarzrohr wurden untersucht. Aus Röntgenbeugungsbildern und Elektronenstrahlmikrosondeanalysen der Produkte folgt, daß sich Phosphidschichten von NiP2 ∼ Ni6P5/Ni2P, Fe2P/(Fe—Ni-Legierung) bilden. Die Phosphidierungen an Legierungen aller Zusammensetzungen verliefen nach dem parabolischen Zeitgesetz. Ein Markierungsversuch zeigte, daß nicht der Phosphor, sondern die Metalle diffundieren. Die Geschwindigkeitskonstante nahm mit zunehmendem Eisengehalt der Legierung ab.
    Additional Material: 8 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 492 (1982), S. 201-207 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Mechanisch initiierte Reaktion des Aluminiums mit AlkylhalogenidenMechanochemische Reaktionen von Aluminium mit Alkylhalogeniden wurden bei Raumtemperatur untersucht. Die Reaktion wurde durch Schwingmahlung ohne Aktivator mechanisch aktiviert. Es wurde gefunden, daß die Reaktionseinleitung nicht auf den Temperaturanstieg während des mechanischen Kontaktes zurückgeführt werden kann, sondern auf die an der Aluminiumoberfläche gebildeten aktiven Zentren durch die Schwingmahlung. Die Reaktivität des gemahlenen Aluminiums war gut zu korrelieren mit der Intensität der Exoelektronenemission. Die Reaktivität und die Emissionsintensität stiegen scharf an nach 60 min Mahlung. Die Abklingcharakteristiken bei Exponierung des voraktivierten Aluminiums wurden für die Reaktivität und Emissionsintensität beobachtet. Die Rolle des Exoelektrons auf die Reaktion wird diskutiert.
    Notes: Mechanochemical reactions of aluminum with alkyl halides were examined at room temperature. The reaction was initiated by mechanical activation of vibromilling without any activator. It was found that the initiation was not due to the temperature rise at mechanical contact but the active sources formed on aluminum surface by vibromilling. The reactivity of milled aluminum was well correlated with the intensity of exoelectron emission. Both the reactivity and the emission intensity increased sharply after 60 min of milling. The decaying characteristics by exposure of preactivated aluminum were observed for both the reactivity and the emission intensity. The role of exoelectron on the reaction was discussed.
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  • 4
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Phasenbeziehungen und Sauerstoff-Nichtstöchiometrie der perowskitartigen Verbindung SrCoOx (2,29 〈 x 〈 2,80)Strontiumcobaltate der Zusammensetzung SrCoO2,29 bis SrCoO2,80 sind unter verschiedenen Bedingungen, in bezug auf Den Sauerstoffdruck und Temperatur, dargestellt worden. Die bei höheren Temperaturen (über 800°C) dargestellten Proben kristallisierten, abhängig vom Sauerstoffdefizit, im Brownmillerit- oder Perowskit-Typ. Eine Perowskit-Phase mit großem Sauerstoff-Defizit, SrCoO2,29, und eine Brownmillierit-feste-Lösung, SrCoOx (2,42 〈 x 〈 2,52) wurden beobachtet. Andererseits kristallisierten bei niedriger Temperatur (unter 800°C) geglühte Proben nicht in der 2H-Typ Struktur mit dem Sr:Co-Verhältnis von 1:1 sondern in der Cobaltdefizit-Phase, 2H-SrCo1-uOx (u ≍ 0,1) und Co3O4. Der sauerstoffreiche Perowskit SrCoO2,67-2,80 wurde durch Glühen der Brownmillerit-Phase unter hohem Sauerstoffdruck bei 300°C Erhalten. Die elektrische Leitfähigkeit von SrCoOx (2,29 〈 x 〈 2,80) und der Sauerstoff-Diffusionskoeffizient der Perowskit-Phase SrCoOx (x = 2,68, 2,75 und 2,80) wurden als Funktion Der Temperatur gemessen. SrCoO2,80 zeigte Den sehr hohen Diffusionskoeffizienten von 2,3 · 10-11 cm2 sec-1 bei 23°C.
    Notes: Strontium cobaltates in the composition range, SrCoO2.29-SrCoO2.80, have been prepared under various conditions with respect to the oxygen pressure and temperature. Samples prepared at high temperatures (above 800°C) crystallized in the brownmillerite or perovskite type Structure Depending on oxygen Deficiency. A perovskite phase having large oxygen Deficiency, SrCoO2.29, and a brownmillerite solid solution, SrCoOx (2.42 〈 x 〈 2.52), were observed. On the other hand, samples annealed at low temperatures (below 800°C) did not crystallize in 2H type Structure with Sr:Co ratio of 1:1 but in the cobalt Deficient phase, 2H-SrCo1-uOx (u ≍ 0.1) and Co3O4. The high oxygen content perovskite SrCoO2.67-2.80 was obtained by annealing the brown-millerite phase under high oxygen pressures at 300°C. The electrical conductivity of SrCoOx (2.29 〈 x 〈 2.80) and the oxygen diffusion coefficient of the perovskite phase SrCoOx (x = 2.68, 2.75 and 2.80) were measured as a function of temperature. SrCoO2.80 showed the very high diffusion coefficient of 2.3 × 10-11 cm2 sec-1 at 23°C.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 18 (1997), S. 1971-1984 
    ISSN: 0192-8651
    Keywords: genetic algorithm ; peptide ; conformer ; enkephalin ; search ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: A genetic algorithm-driven search method (GAP1.0; Genetic Algorithm Peptide search, version 1.0) has been developed for the computational exploration of peptide conformational space. The suitability of a variety of genetic algorithm operators was evaluated through representative calculations on the pentapeptide [Met]-enkephalin (Tyr-Gly-Gly-Phe-Met). GAP1.0 was successful in efficiently elucidating backbone conformational features observed in the global minimum energy structure. Furthermore, the program readily identified the tremendous diversity among [Met]-enkephalin conformers under physiological conditions. It is concluded that GAP1.0 provides a useful extension to the current repertoire of conformational analysis techniques.   © 1997 John Wiley & Sons, Inc.   J Comput Chem 18: 1971-1984, 1997
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1216-1224 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterosubstituted Acetylenes, XXX1). A new Mechanism of Nucleophilic Halogen Substitution at Acetylene Triple BondsThe combination of nucleophilic and directiospecific addition in β-position to halogen 1) (except fluorine) with subsequent onium rearrangement is proposed as a new mechanism of nucleophilic halogen substitution at the acetylene triple bond. The reactions of chloro-tertbutyl-acetylene (1) with phenolate and thiophenolate are described as examples. The β-adducts 2,5 und 6 are formed directiospecifically. 5 and 6 give rise photochemically and thermally to the thermodynamically more stable isomer 8 in which the chlorine atom and the thioether residue have migrated and changed their C-atoms. All thioether isomers produce the tert-butylethinyl-thioether 10 upon elimination of HCl.
    Notes: Die Kombination von nucleophiler directiospezifischer Addition in β-Stellung zum Halogen1) (außer Fluor) mit anschließender Onium-Umlagerung 2) und Halogen-Anion-α-Eliminierung wird als neuer Mechanismus der nucleophilen Halogensubstitution an der Acetylendreifachbindung vorgeschlagen. Als Beispiel für diese Reaktionsschritte werden die Umsetzungen von Chlor-tert.-butyl-acetylen (1) mit Phenolat und mit Thiophenolat beschrieben. Directiospezifisch entstehen die β-Addukte 2,5 und 6. Thermisch und photochemisch bildet sich aus 5 und 6 das thermodynamisch stabilere Isomere 8, in welchem Chlor und der Thioätherrest unter Vertauschung der C-Atome gewandert sind. Alle Thioäther-Isomeren liefern bei der HCl-Abspaltung den tert.-Butyläthiny-thioäther 10.
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  • 7
    ISSN: 0009-2940
    Keywords: Thioether, benzyl ; Mercapto amines ; Nickel complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Addition of two equivalents of benzyl bromide to [N,N′-bis(2-mercaptoethyl)-1,5-diazacyclooctane]nickel(II) (Ni-1) produced the green dibenzyl dithioether complex [Ni-1-Bzl2Br2] structurally characterized by X-ray crystallography as a six-coordinate octahedral complex in a monoclinic crystal system and the P21/c space group. Benzylation of the methyl thioether/thiolate [(Ni-1-Me)+I- yielded the mixed benzyl/methyl dithioether [(Ni-1-BzlMe)Br]I, structurally characterized by X-ray crystallography as a five-coordinate square pyramidal nickel(II) complex with a Ni-Br distance of 2.451 Å. The complex crystallizes in the orthorhombic Cmca space group. The latter is the first nickel(II) pentacoordinate complex isolated for the N,N′-bis(2-mercaptoethyl)-1,5-diazacyclooctane (daco) ligand. Structural comparison of these two complexes with the square-planar dimethyl compound [Ni-1-Me2]I2 found an expansion of the N2S2 plane upon addition of axial ligands. The five-coordinate nickel complex showed a displacement of the Ni ion from the N2S2 plane by 0.43 Å toward the axial bromide ligand, a common observation of pentacoordinate complexes of this ligand with metals such as Zn and Fe. Electrochemical studies as well as the X-ray crystal structures for complex [Ni-1-Bzl2Br2] and [(Ni-1-BzlMe)Br]I are presented and discussed in detail.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1209-1215 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterosubstituted Acetylenes, XXIX. „Onium“ -Rearrangements to disubstituted Acetylenes: The Synthesis of Yne Diamines2-Fluoro-1.1-dichloroethylene (1) or trichloroethylene reacts with N. N-disubstituted lithiumamides and sec. amines to form chloroketene aminals (7). Upon treatment with strong bases the latter undergo HCl α-elimination and „onium:“ rearrangement to afford yne diamines 3 in high yields. Phenyl-ynamine 10 can also be prepared in the same manner from phenylchloroenamine 9 but it is not clear whether the amino group or the phenyl residue migrates. The synthesis of the tert-butylethinyl-thioether (13) from 1-chloro-2-phenylthio-3, 3- dimethylbut-1-ene 12 shows the onium rearrangement of thioether group.
    Notes: Aus 2-Fluor-1.1-dichlor-äthylen (1) oder aus Trichloräthylen entstehen mit N.N-disubstituierten Lithiumamiden und sek. Aminen die Chlorketen-aminale 7. Diese liefern mit starken Basen durch α-HCl-Abspaltung und „Onium“-Umlagerung in hoher Ausbeute In-diamine 3. Nach diesem Verfahren läßt sich auch das Phenyl-inamin 10 aus dem phenylchlorenamin 9 darstellen, ohne daß vorläufig entschieden werden konnte, ob die Aminogruppe oder der phenylrest wandert. Die Synthese des tert. -Butyläthinyl-phenyl-thioäthers (13) aus 1-Chlor-2-phenylmercapto-3.3-dimethyl-buten-(1) (12) belegt die Onium-Umlagerung einer Thioäther-Gruppe.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 1198-1208 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Heterosubstituted Acetylenes, XXVIII1) Directiospecific Additions and Substitutions with Fluorochloroacetylene2) and 2-Fluoro-1.1-DichloroethyleneFluorochloroacetylene (2), a very unstable explosive compound, is formed from 2-fluoro-1.1-dichloroethylene (1). 2 adds diethylether directiospecifically, with the ether group in β-position to the chlorine atom. The directiospecificity of the addition and substitution reactions of 2 is explained on the basis of d-orbital resonance of the chlorine atom and stabilisation of the intermediate α-vinyl radicals and anions.  -  Thiophenolate reacts with 1 to form 1-fluoro-2-chloro-1-phenylthioethylene (13) probably by addition to 1 and subsequent elimination.  -  1 affords the lithium derivative 14, which is thermally more stable than trichlorovinyl lithium. 14 reacts with lithium-N-methylanilid to form the chloro ynamine 17, possibly via the intermediate 2. The adducts of 17 with sec. amines are chloroketene aminals 16, which on treatment with bases yield yne diamines 3.
    Notes: Fluorchloracetylen (2) entsteht aus 2-Fluor-1.1-dichlor-äthylen (1) als äußerst instabile, explosive Verbindung. 2 addiert Diäthyläther directiospezifisch mit dem Ätherrest in β-Stellung zum Chlor. Die Directionspezifität der Additions- und Substitutionsreaktionen von 2 wird durch d-Orbitalresonanz des Chlors und Stabilisierung der intermediären α-Vinyl-Radikale und -Anionen gedeutet.  -  Thiophenolat reagiert mit 1 unter Bildung von 1-Fluor-2-chlor-1-phenylmercapto-äthylen (13), wahrscheinlich unter Addition an 1, gefolgt von Eliminierung.  -  1 liefert das Lithiumderivat 14, das thermisch etwas stabiler ist als Trichlorvinyllithium. Aus 14 entsteht, möglicherweise über intermediäres 2, mit Lithium-[N-methyl-anilid] das Chlor-inamin 17, dessen Addukte mit sek. Aminen die Chlorketen-aminale 16 sind, die mit Basen die In-diamine 3 liefern.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 34 (1903), S. 86-102 
    ISSN: 0863-1778
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 6 Ill.
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