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  • Inorganic Chemistry  (554)
  • Wiley-Blackwell  (554)
  • Elsevier
  • Oxford University Press
  • 1995-1999  (112)
  • 1990-1994  (420)
  • 1945-1949  (22)
  • 1
    Electronic Resource
    Electronic Resource
    Complexation with Diol Host Compounds, 12. Synthesis and Solid-State Inclusion Properties of Bis(diarylhydroxymethyl)1-Substituted 1,1′-Binaphthyls. Crystal Structures of a Host and Its Pyridine Clathrate (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1141-1148 
    Details
    ISSN: 0009-2940
    Keywords: Diol host compounds ; Clathrates ; Crystal structures of host and clathrate ; 1,1′-Binaphthyl derivatives ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of new clathrate host molecules 1 - 8 containing two bis(diarylhydroxymethyl) groups attached to different positions (2,2′ or 8,8′) of a 1,1′-binaphthyl frame have been synthesized. Their clathrate formation properties with organic guests including alcohols, amines, ketones, and other dipolar aprotic compounds or aromatic hydrocarbons are reported (74 examples of clathrates) together with the results of solvent competition experiments for the parent host compound. The inclusion formation and the clathrate stoichiometries depend on the structure of the host molecules in a systematic manner. The crystal structures of the free parent host 1 and its pyridine clathrate (1 : 3) have been determined by X-ray diffraction. The molecular structure of the host is similar in the two species involving an intramolecular hydrogen bond between the host hydroxyls. No other hydrogen bond is involved in the free host case while in the pyridine inclusion compound the second host hydroxyl forms a hydrogen bond with the nitrogen of one pyridine guest which is surrounded by two unbound pyridine species such as to form clusters of three pyridine guests enclosed in the cavities between the host molecules. Thermal analysis corresponds with the two binding states of the pyridine molecules in the clathrate.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19931260513
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  • 2
    Electronic Resource
    Electronic Resource
    Collisionally Activated Dissociation of Some Bulkily Substituted Pyridinium Cations, II. Substituent Effect on Appearance Potential (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 177-181 
    Details
    ISSN: 0009-2940
    Keywords: Gas-phase dissociation ; Appearance energies ; Calculations, AM1 ; Pyridinium cations, N-benzyl-2,4,6-substituted ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Collisionally activated dissociations (CADs) of various pyridine-ring substituted N-benzylpyridinium cations in the gas phase form the substituted pyridine and benzyl carbocation. Appearance energies (AEs) are estimated quantitatively from the appearance thresholds of the corresponding fragment ion from the laser-desorbed pyridinium cations. MO calculations predict that such unimolecular dissociation processes lead initially to ion-molecule pairs (IMPs): some such IMPs are of significantly lower energy than the fully dissociated products. The AEs have also been compared with the energy differences [ΔΔHf=ΔHf(Py) + ΔHf(R+)  -  ΔHf(Py+R)] determined by AM1 calculations: in many cases these are quite close to the calculated energy differences; discrepancies are discussed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19921250129
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  • 3
    Electronic Resource
    Electronic Resource
    Spektroskopischer Nachweis eines Bis(amino)silylens (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 1375-1377 
    Details
    ISSN: 0009-2940
    Keywords: Silicon(IV) diazide ; Photolysis ; Matrix isolation ; Silylene, bis(amino)- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Spectroscopic Identification of a Bis(amino)silyleneThe photolysis of the silicon diazide 3a in benzene solution and in an Ar matrix is described. Both irradiations cause the elimination of 3 equivalents of N2. Loss of N2 from 3a in benzene leads to the formation of the analytically investigated product or products 4 of uncertain structure. However, the matrix photolysis of 3a results in a compound which is stable up to 77 K and has been identified as the bis(amino)silylene 2d by comparison of its IR spectra with those of the homologous Sn and Ge compond.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19921250611
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  • 4
    Electronic Resource
    Electronic Resource
    A Phosphine Complex of Bismuth(III): X-ray Crystal Structure of [PMe3H][Bi2Br7(PMe3)2] (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 2457-2459 
    Details
    ISSN: 0009-2940
    Keywords: Bismuth complexes ; Phosphine ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction between BiBr3 and one equivalent of PMe3 in THF affords, after recrystallisation from MeCN/Et2O, yellow crystals of [PMe3H][Bi2Br7(PMe3)2]. 2 (MeCN) (1), which has been characterised by X-ray crystallography. Compound 1 is the first reported bismuth-phosphine complex and comprises a polymeric anion, the monomeric unit of which contains a planar Bi2Br6 core, each bismuth being further bonded to a PMe3 ligand and an additional bromide such that the bismuth resides in an octahedral coordination environment. The latter bromides form linear bridges between monomeric units; the phosphines are trans with respect to the Bi2 unit, with a Bi-P distance of 2.762(3) A. The reaction between Bil3 and PEt3 in THF affords, after recrystallisation from MeCN/Et2O, orange crystals of [PEt4]4[Bi6I22] (3) which has also been characterised by X-ray crystallography.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911241115
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  • 5
    Electronic Resource
    Electronic Resource
    The Pagodane Route to Dodecahedranes Directed Conversions - The Pagodane → Bissecododecahedradiene StageDedicated to Prof. Dr. William von E. Doering on the occasion of his 75th birthday. (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 1697-1717 
    Details
    ISSN: 0009-2940
    Keywords: Pagodane → dodecahedrane pathways ; Pagodane opening reactions ; Cage effects ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three conceptual routes (A, B, C) from [1.1.1.1]pagodane (1) to pentagonal dodecahedrane (2) are evaluated by MM2 (MM3) calculations. After limited experimental success with a catalytic one-pot route (A), a more selective transformation along one of two stepwise routes (B/C) is explored. An expeditious entry into route C is achieved by hydrogenolytic cyclobutane opening in 1; secopagodane 7 (100%), however, resists both progression along route C (dehydrogenative C - C bond formation to isododecahedrane 8) and crossover into route B (hydrogenolysis to bissecododecahedrane 5). The first transformation along route B, the 2sigma;→2π-isomerization of the highly strained 1 to bissedodecahedra-1,10(11)-diene 3, is not attainable by metal catalysis and cannot productively be brought about by thermal activation: The necessarily very high reaction temperatures (〉 700°C) enforce instead a mechanistically interesting fragmentation into two C10H10 halves to give ultimately naphthalene. The very rapid pagodane opening occurring after one-electron oxidation, too, is not a preparatively useful alternative. Highly efficient, on the other hand, is a two-step process affording a high yield of the product and consisting of regiospecific, photochemically induced bromine addition to the central four-membered ring (→ dibromosecopagodane 37) followed by reductive bromine elimination (→ diene 3). In spite of the necessarily rather severe reaction conditions in both steps, this procedure is applicable to the preparation of various 3,8-difunctionalized bissecodienes (dienedione 11, diene diesters 43, 50, 52, dichlorodiene 56). Limitations of this procedure are met with the 4,4,9,9-tetrachloropagodane 60 (inert) and the [2.2.1.1]pagodane 80 (bridgehead bromination). The lateral half-cages of the (seco)-pagodane structures are explored for preparatively (dis)advantageous steric effects, that might be later exploited on the way towards functionalized dodecahedrane derivatives.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19921250727
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  • 6
    Electronic Resource
    Electronic Resource
    The Pagodane Route to Dodecahedranes Unsaturated (Hyperstable) and Saturated BissecododecahedranesDedicated to Prof. Dr. Günther Maier on the occasion of his 60th birthday (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 1719-1739 
    Details
    ISSN: 0009-2940
    Keywords: Bissecododecahedranes, saturated, unsaturated ; Homoconjugation ; Hyperstability ; Addition reactions ; Cage effects ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In bissecododecahedra-1,10(11)-dienes, the syn-periplanar and unusually proximate arrangement of the π bonds is responsible for extraordinary physical properties such as strong throughspace homoconjugation, low oxidation potentials, and a special reactivity pattern. In pursuit of route B to dodecahedranes[1], the hyperstability predicted (MM2) for these bissecodienes and the related monoenes has been experimentally verified only for the latter in their resistance towards catalytic hydrogenation. Non-hydrogenative saturation of (3,8-difunctionalized) bissecodienes (3, 8, 13) and monoenes (4, 9, 14) becomes increasingly hampered due to the increased steric congestion on the more spherical molecular surfaces but can be achieved in „high-driving-force” reactions [cis-hydroxylation (26, 27, 41, 42), epoxidation (38, 54, 57, 58, 60, 63, 80, 83), cyclopropanation (55, 59, 61, 64]. In contrast, cycloadditive four-, five- (73), and six-membered (76) ring annulation again is limited to monoadditions. The half-cages in the bissecododecahedrane structures provide for remarkable steric steering and protection [e.g. anti-selective protonation (alkylation) of carbanions 57a (84a)2-, lack of hydrazone formation from ketones 58, 89, resistance of syn-bis(acid chloride) 86 towards hydrolysis.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19921250728
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  • 7
    Electronic Resource
    Electronic Resource
    The Pagodane Route to Dodecahedranes Scope and Limitation of the Dehydrocyclization StratagemDedicated to Prof. Dr. George A. Olah on the occasion of his 65th birthday. (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 1741-1751 
    Details
    ISSN: 0009-2940
    Keywords: Bissecododecahedranes, hydrogenolysis, catalytic dehydrocyclization ; Dodecahedranes ; Cyclizations, non-dehydrogenative ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stepwise route B from pagodanes to dodecahedranes was completed by double catalytic dehydrocyclization of saturated (alkylated) bisseco precursor substrates (2, 3, 5, 16). Based on pagodane, dodecahedranes (9, 10, 13, 14, 17) were obtained in up to 53% yield. Transannular C,C bond formation at the bisseco stage and partial (C-alkyl) or total (C-OR, C-CO2R) removal of substituent groups under the necessarily forcing reaction conditions constituted preparative limitations. Attempts at alternative ring closure methodologies (homo-Norrish type II, homoenolization, carbene insertion) have remained unsuccessful.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19921250729
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  • 8
    Electronic Resource
    Electronic Resource
    Crystal Structure of a Representative Mixed Adduct of Trimethylaluminium and a Lithium Amide and a Theoretical MO Study on Model Systems (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1293-1300 
    Details
    ISSN: 0009-2940
    Keywords: Calculations, ab initio ; Aluminium compounds ; Heterometallic compounds ; Lithium compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of the simple alane adduct [Me3Al · HN(CH2Ph)2] (2) with the lithium amide [(PhCH2)2NLi] leads to the formation of the mixed adduct [Me3Al · (PhCH2)2NLi · HN(CH2Ph)2] (1). The crystal structures of 1 and 2 are reported. Exhibiting a four-membered, mixed-metal, mixedanion ring-core, the structure of 1 is unusual in containing a monomeric lithium dibenzylamide fragment. Such fragments generally convert to aza-allyl derivatives, so its existence here can be attributed to the stabilising effect of the attached Me3Al ligand. Crystalline 2 adopts the classical, distorted-tetrahedral arrangement of simple monomeric alane adducts. Ab initio MO calculations on model systems show that mixed adduct formation from Me3Al and Me2NLi is exothermic, while further reaction to give Me2AlNMe2 and MeLi (i.e., complete transmetallation) is endothermic.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961291024
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  • 9
    Electronic Resource
    Electronic Resource
    Voltammetrische und spektroskopische Untersuchungen zur Komplexbildung von Vanadium(IV) und Vanadium(V) mit CarbonatProfessor Lothar Kolditz zum 60. Geburtstage gewidmet (1990)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 583 (1990), S. 209-222 
    Details
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Voltammetric and Spectroscopic Investigation of Complexation of Vanadium(IV) and Vanadium(V) by CarbonateSolutions which contain in addition to vanadium(IV) or vanadium(V), respectively, a high excess of bicarbonate or carbonate were studied by voltammetric and spectroscopic methods.A reversible electrode reaction occurs in the pH range 7-8 in 1 M KHCO3. While generating VIV from VV electrochemically a carbonate ligand is added to VIV. Based on ESR parameter recorded at room temperature and 77 K the existence of a VIV carbonato complex is suggested. A comparison of these ESR parameter with those of analogous VIV complexes leads to conclusions in view of the structure of the VIV carbonato complex.These structural suggestions are supported by the fact that VIV and VV form a mixed valent dimer in HCO3-/CO2-buffer of pH 7.5. Such dimers can be formed only when one of the oxygens of the VVO2+ cis-dioxo unit is able to coordinate at a basal site in the VIV-complex. Thus, conclusions regarding the arrangement of the carbonato ligands in the monomeric VV complex are possible too.A comparison of the complexes which are formed by VIV and VV with carbonate and the adducts arising from the interaction of VIV and VV with transferrin reveals the similarities of the both redox couples.
    Notes: Es wurden Lösungen mit Vanadium(IV) sowie Vanadium(V) bei Anwesenheit eines hohen Überschusses an Hydrogencarbonat bzw. Carbonat voltammetrisch und spektroskopisch untersucht. In 1 M KHCO3 trifft man im pH-Bereich 7-8 auf eine reversible Elektrodenreaktion VV/VIV, die von der Anlagerung eines Carbonatliganden beim Übergang VV → VIV begleitet wird.Auf der Basis der bei Raumtemperatur und 77 K erhaltenen ESR-Parameter wird die Existenz eines VIV-Carbonatokomplexes postuliert. Durch Vergleich der ESR-Parameter dieses Komplexes mit denen analoger VIV-Komplexe werden Schlußfolgerungen hinsichtlich seiner Struktur gezogen. Dieser Strukturvorschlag läßt sich durch die Tatsache stützen, daß VIV und VV im HCO3-/CO2-Medium (pH = 7,5) ein gemischtvalentes Dimer bilden.Solche Dimere treten nur auf, wenn eines der beiden Oxo-Sauerstoffatome der VVO2+-Gruppierung des VV-Komplexes an einer vakanten Koordinationsstelle in cis-Position zur VIV-Sauerstoff-doppelbindung im VIV-Komplex koordinieren kann. In diesem Zusammenhang ergibt sich auch die Möglichkeit, Schlußfolgerungen bezüglich der Anordnung der Carbonatliganden im monomeren VV-Komplex zu ziehen.Eine vergleichende Betrachtung der Komplexe, die VIV und VV mit Carbonat bilden und den Assoziaten des VIV als VV mit Transferrin läßt die Ähnlichkeiten dieser beiden korrespondierenden Redoxpaare deutlich werden.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19905830126
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  • 10
    Electronic Resource
    Electronic Resource
    Zur Darstellung und Struktur von LaNb5O14 (1990)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 583 (1990), S. 223-223 
    Details
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19905830128
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