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  • 1
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Nuclear Magnetic Resonance Studies on Boron Compounds, XIV. Indirect Nuclear Spin-Spin Coupling of 11B with other Directly Bonded NucleiCoupling constants 1J(11BX) and chemical shifts δ11 B and δX are reported for X = 1H, 13C, 15N, 19F, 29Si, 31P, 77Se, 119Sn, and 207Pb. The signs of 1J(11B29Si)(negative) and 1J(11B31P) (positive) in compounds of tervalent boron have been determined by double resonance experiments 1H-{11B} and 13C-{X}. With the exception of X = 19F, the magnitude and sign of 1J(11BX) can be interpreted by assuming a dominating Fermi contact term in the coupling mechanism. The possible influence of the spin-dipole and the orbital term on the magnitude of the coupling is discussed.
    Notes: Kopplungskonstanten 1J(11BX) mit X = 1H, 13C, 15N, 19F, 29Si, 31P, 77Se, 119Sn und 207Pb sowie chemische Verschiebungen δ11 B und δX wurden bestimmt. Die Vorzeichen von 1J(11B29Si) (negativ) und 1J(11B31P) (positiv) in Verbindungen des dreibindigen Bors folgten aus Doppel-resonanzexperimenten 1H-{11B} and 13C-{X}. Ausgenommen X = 19F, sind Größe und Vorzeichen von 1J(11BX) mit der Annahme zu erklären, daß der Fermi-Kontaktterm im Kopplungs-mechanismus dominiert. Der mögliche Einfluß des Spin-Dipol- und des Orbital-Terms auf die Größe der Kopplung wird diskutiert.
    Additional Material: 5 Tab.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 111 (1978), S. 3596-3607 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, XCVI: N-Metallation of N-Substituted Aminodimethylboranes by Organolithium ReagentsThe Lewis acidity of the (CH3)2BN group gains weight versus the proton acidity of the NH group in the series (CH3)2B—NH—N(CH3)2 (1), (CH3)2B—NH—Si(CH3)3 (4), (CH3)2B—NH—B(CH3)2 (7). N-Lithio derivatives (2, 5) can therefore be prepared only from 1 and 4. In the reaction of 1, 4, and 7 with LiCH3 NMR spectroscopy reveals the formation of [(CH3)3B—NHR]Li (3, 6, 8) as intermediates. From these 3 and 6 evolve CH4 to give 2 and 5, respectively, while 8 decomposes into LiB(CH3)4 and the borazine (CH3BNH)3. A bond order 〉 1 for the B—N bond is indicated by the NMR data of the N-lithioaminoboranes 2 and 5, and according to mass spectral data 5 seems to be hexameric, however 2 is most likely polymeric.
    Notes: In der Reihe (CH3)2B—NH—N(CH3)2(1), B—NH—Si(CH3)2B—NH—B(CH3)2 (7) gewinnt die Lewis-Acidität der (CH3)2BN-Gruppe im Vergleich zur Protonenacidität der NH-Gruppe gegenüber Lithiumorganylen zunehmend an Gewicht. N-Lithioderivate (2, 5) sind nur mehr von 1 und 4 darstellbar. NMR-spektroskopisch ist bei allen Reaktionen mit LiCH3 die Boratstufe [(CH3)3B—NHR]Li (3, 6, 8) nachweisbar, die bei 3 und 6 unter Methanabspaltung, bei 8 hingegen zu LiB(CH3)4 und (CH3BNH)3 zerfällt. Die NMR-Spektren der N-Lithioaminoborane 2 und 5 belegen eine Bindungsordnung 〉 1 für die B—N-Bindung. Nach Massenspektren dürfte 5 hexamer und 2 polymer aufgebaut sein.
    Additional Material: 1 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 114 (1981), S. 2723-2730 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron 118. Structure and Dynamics of Hexamethylborazine-Aluminium TribromideAluminium tribromide in its 1:1 adduct with hexamethylborazine coordinates with one nitrogen atom. This results in a loss of the planarity of the borazine ring system, and the BN bond lengths vary now from 139 to 154 pm as shown from an X-ray crystal structure determination of the monoclinic adduct (Rw = 0.076). The ring conformation is additionally influenced by weak intramolecular and intermolecular Br-B interactions. The adduct shows fluctional behaviour in solution at temperatures higher than 276 K.
    Notes: Aluminiumbromid koordiniert in seinem 1: 1-Addukt mit Hexamethylborazin über ein N-Atom Der Borazin-Ring verliert dadurch seine Planarität, seine BN-Abstände variieren zwischen 139 und 154 pm, wie aus der Röntgenstrukturanalyse des monoklin kristallisierenden Addukts her-vorgeht (Rw = 0.076). Die Ringkonformation wird durch schwache intramolekulare und intermolekulare Br-B-Wechselwirkungen geprägt. In Lösung zeigt das Addukt fluktuierendes Verhalten oberhalb von 276k.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 3829-3841 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, LXXXVIII. N-Metalation of Dimethyl(methylamino)borane by Organolithium ReagentsThe N-lithiation of (CH3)2B—NHCH3 (1) by organolithium reagents LiR is characterized by a solvent-dependent competition between the deprotonation to (CH3)2B—NLiCH3 (2) and the carbanion addition to the Lewis-acidic boron atom to yield Li[(CH3)2RB—NHCH3] 3.3 (R=CH3) decomposes slowly to form CH4 and 2. Moreover, 1 reacts with 2 to give (CH3BNCH3)3 (6) and Li[B(CH3)4] (4).  -  Pure 2 is obtained from 1 and tert-butyllithium in pentane solution, and the 1:1 adduct of 2 with N,N,N′,N′-tetramethylethylenediamine (TMEDA) is formed from 1 and LiCH3 in the presence of TMEDA. NMR spectra indicate the structure of these compounds.
    Notes: Die N-Lithiierung von (CH3)2B—NHCH3 (1) mit Lithiumorganylen LiR führt in einer lösungsmittelabhängigen Konkurrenzreaktion unter Deprotonierung zu (CH3)2B—NLiCH3 (2) und unter Carbanion-Addition an das Lewis-saure Bor-Atom zu Li[(CH3)2RB—NHCH3]3.3(R=CH3) zersetzt sich langsam in CH4 und 2. In einer Folgereaktion setzt sich 1 mit 2 zu (CH3BNCH3)3 (6) und Li[B(CH3)4] (4) um.  -  Reines 2 erhält man aus 1 und tert-Butyllithium in Pentan, das 1:1-Addukt aus 2 und N,N,N′,N′-Tetramethylethylendiamin (TMEDA) aus 1 und LiCH3 in Gegenwart von TMEDA. NMR-Spektren geben Hinweise auf die Konstitution dieser Verbindungen.
    Additional Material: 3 Tab.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 3672-3681 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, CIII. A Dimeric Diazastannaboretidine: Preparation, Dynamic Behaviour, and Molecular Structure(CH3)2B-N(CH3)Li and SnCl2 yield unstable Sn[NCH3-B(CH3)2]2; however, the reaction of SnCl2 with (CH3)3Si-NLi-B(CH3)2 leads to the dimeric diazastannaboretidine 4b with elimination. of B(CH3)3. 4b shows fluctuating behaviour at 〉60°C. According to its X-ray structure, 4b possesses a tricyclic tub form structure built from three condensed four-membered rings.
    Notes: (CH3)2B-N(CH3)Li und SnCl2 liefern instabiles Sn[NCH3-B(CH3)2]2, während die Umsetzung von SnCl2 mit (CH3)3Si-NLi-B(CH3)2 unter B(CH3)3-Abspaltung zu dem dimeren Diazastannaboretidin 4b führt. Dieses System zeigt oberhalb von 60°C fluktuierendes Verhalten. Nach einer Röntgenstrukturanalyse besitzt 4b eine tricyclische, aus drei Vierringen bestehende Wannen-struktur.
    Additional Material: 2 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 113 (1980), S. 728-738 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, CV. (N-Lithiomethylamino)dimethylborane as a Reagent for the Preparation of N-Functional AminodimethylboranesThe reagent (CH3)2 — N(CH3)Li (1) allows the synthesis of many borylaminoelement compounds such as (CH3)2B — NCH3 — BCH3 — N(CH3)2, (CH3)2Si[NCH3 — B(CH3)2]2, (CH3)2B - NCH3 — Si(CH3)2 — NCH3 — Si(CH3)2Br, (CH3)2B — NCH3 — P(CH3)2 or (CH3)2B — NCH3 — As(CH3)2. Multifunctional element halides cause the formation of a complex mixture of products, and this is in part due to cyclocondensation reactions of longer chain compounds.
    Notes: Das Reagens (CH3)2B — N(CH3)Li (1) ermöglicht die Synthese zahlreicher Borylaminoelement-Verbindungen wie (CH3)2B — NCH3 — BCH3 — N(CH3)2, (CH3)2Si[NCH3 — B(CH3)2]2, (CH3)2B — NCH3 — Si(CH3)2 — NCH3 — Si(CH3)2Br, (CH3)2B — NCH3 — P(CH3)2 oder (CH3)2B — NCH3 — As(CH3)2. Mit mehrfunktionellen Elementhalogeniden wird die Produktpalette komplexer, was auch auf Cyclokondensation der längerkettigen Verbindungen zurückzuführen ist.
    Additional Material: 1 Ill.
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  • 7
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, 112. Molecular and Crystal Structure of a Series of Five-Membered 6 π-Electron Heterocycles with Boron, Sulfur, and Nitrogen as Ring MembersThe crystal and molecular structures of 3,4,5-trimethyl-1,2,4,3,5-dithiazadiborolidine (2), 2,3,4,5-tetramethyl-1,3,4,2,5-thiadiazadiborolidine (3), and 3,5-dichloro-1,2,4-trimethyl-1,2,4,3,5-triazadiborolidine (5) have been determined. A planar ring structure was found for 2 and 3 like that of 3,5-dimethyl-1,2,4,3,5-trithiadiborolane (1) and 1,2,3,4,5-pentamethyl-1,2,4,3,5-triazadiborolidine (4). Therefore, these heterocycles can be described as five-membered 6 π electron systems. In contrast to 2 and 3, 5 forms a tricyclic system in the solid state and is present as a dimer. The structures of 1 to 5 are compared.
    Notes: Die Kristall- und Molekülstrukturen von 3,4,5-Trimethyl-1,2,4,3,5-dithiazadiborolidin (2), 2,3,4,5-Tetramethyl-1,3,4,2,5-thiadiazadiborolidin (3) sowie von 3,5-Dichlor -1,2,4-trimethyl-1,2,4,3,5-triazadiborolidin (5) wurden bestimmt. 2 und 3 besitzen ebenso wie 3,5-Dimethyl-1,2,4,3,5-trithiadiborolan (1) und 1,2,3,4,5-Pentamethyl-1,2,4,3,5-triazadiborolidin (4) ein planares Ringgerüst. Sie können als fünfgliedrige 6 π-Elektronensysteme aufgefaßt werden. Im Gegensatz zu 2 und 3 liegt 5 im festen Zustand als Dimeres in Form eines tricyclischen Systems vor. Die Strukturen werden vergleichend diskutiert.
    Additional Material: 5 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 2542-2546 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Contributions to the Chemistry of Boron, 142. Some Substitution Reactions of 1,3-Dimethyl-1,3,2-diazaborolidines and the Anomalous Dimerisation of its 2-Fluoro DerivativeThe transamination of B[N(CH3)2]3 with α,ω-dimethylalkylenediamines proceeds via the bridged species 2 and 3. These react with boron halides to yield 2-halo-diazaborolidines. The 2-fluoro derivative 6 has been obtained from fluorination of the 2-methylthio compound with SbF3. 6 dimerizes in an anomalous fashion yielding a fluxional tricyclic species.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 1931-1938 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, LXXXIII. The Anomalous Dimerisation of 3,5-Difluoro-1,2,4-trimethyl-1,2,4,3,5-triazadiborolidineSbF3- or BF3-fluorination of 3,5-bis(methylthio)- (1e) or 3,5-bis(dimethylamino)-1,2,4-trimethyl-1,2,4,3,5-triazadiborolidine (1c) leads to formation of the difluoro derivative 1a which is dimeric (3a). The „anomalous“ dimerisation, involving fluoride migration, is deduced from n. m. r. spectra and has been confirmed by X-ray crystallography of the dimer: it contains the structure elements BN4 and N2BF2.
    Notes: Das durch SbF3-bzw. BF3-Fluorierung von 3,5-Bis(methylthio)-(1e) bzw. 3,5-Bis(dimethylamino)-1,2,4-trimethyl-1,2,4,3,5-triazadiborolidin (1c) darstellbare Difluorderivat 1a liegt dimer als 3a vor. Die aus NMR-Spektren ableitbare „anomale“ Dimerisierung, die mit einer Fluorid-Wanderung verbunden ist, wird durch die Röntgenstrukturanalyse des Dimeren bestätigt: dieses enthält BN4- und N2BF2-Strukturelemente.
    Additional Material: 1 Ill.
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  • 10
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Contributions to the Chemistry of Boron, CIV. New Ring Systems Containing Diboron Units: Dithiadisilaboracyclopentanes, Dithiatriborolanes, and DithiatetraborinanesThe pyridine-catalysed comproportionation between the cyclothiasilanes 1 or 4 and the dithiatetrasilacyclohexane 2 yields the dithiatrisilacyclopentane 3. 3 reacts with R2N(Cl)B - B(Cl)NR2 (5), and the R2Si - SiR2 group is specifically eliminated from 3 yielding the dithiasiladiboracyclopentane 6, which is also obtained from 5 and 1 or 4, respectively. Further action of 5 on 6 results in the dimethylamino derivative of a dithiatetraborinane (7). Moreover, a dithiadisilaboracyclopentane (8) results from the S2Si4 system 2 and phenylborane dichloride, and finally, a dithiatriborolane (10) is obtained from 6 and CH3B(SCH3)2. The new heterocyclic compounds were fully characterized chemically and spectroscopically. The X-ray structure analysis of 6 and 7 reveals nonplanar rings with short B — N bonds.
    Notes: Die mit Pyridin katalysierte Komproportionierung der Cyclothiasilane 1 und 4 mit dem Dithiatetrasilacyclohexan 2 liefert das Dithiatrisilacyclopentan 3. Dieses reagiert spezifisch mit R2N(Cl)B - B(Cl)NR2 (5) zu einem Dithiasiladiboracyclopentan (6), ebenfalls erhältlich aus 5 und 1 bzw. 4. Mit weiterem 5 setzt sich 6 zum Dimethylamino-Derivat eines Dithiatetraborinans (7) um. Ein Dithiadisilaboracyclopentan (8) entsteht aus dem S2Si4-System 2 und Phenylbordichlorid, ein Dithiatriborolan-Derivat (10) aus 6 und CH3B(SCH3)2. Die neuen Heterocyclen werden chemisch und spektroskopisch charakterisiert. Die Röntgenstrukturanalyse sicherte für 6 und 7 nichtplanare Ringsysteme mit kurzen B — N-Bindungen.
    Additional Material: 2 Ill.
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