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  • 1975-1979  (14)
  • 1977  (14)
  • Chemistry  (14)
  • Alanes
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  • 1975-1979  (14)
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  • 1
    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.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 1086-1094 
    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, XII. 1H-, 11B-, 13C-, and 14N-Nuclear Magnetic Resonance Studies on Alkinylboranesπ-Back bonding of the CC-triple bond to boron accounts for δ11 B and δ13C of alkinylboranes (1 - 20, tables 1, 2). δs14 N-data support this interpretation. The diamagnetic anisotropy of the CC-triple bond is responsible for an additional high field shift of δ11B compared with those of alkenylboranes. - The magnitude and sign of the coupling constant 1J(13C11 B) in (C2H5)2 N - B-(C≡CH)2 has been determinded by means of double resonance measurements 1H{11B}. δ1 H of the ethinylic protons depends on anisotropic and mesomeric effects.
    Notes: δ11 B- und δ13C-Werte von Alkinylboranen (1-20, Tab. 1, 2) legen eine π-Rückbindung der CC-Dreifachbindung zum Bor-Atom nahe. δ14 N-Daten stützen diese Interpretation. δ11 B ist infolge des Anisotropieeffektes der benachbarten Dreifachbindung stärker hochfeldverschoben als in Alkenylboranen. - Größe und Vorzeichen der Kopplungskonstante 1J (13C11B) in (C2H5)2N - B(C≡CH)2 wurden mit Hilfe von Doppelresonanzmessungen 1H{11B} bestimmt. δ1 H der Ethinylprotonen wird vom Anisotropieeffekt und vom mesomeren Effekt kontrolliert.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 1643-1650 
    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, LXXX. Aminolysis of Dimethyltrithiadiborolane with Primary AminesPrimary amines react with 3,5-dimethyl-1,2,4,3,5-trithiadiborolane (1) by ring-opening followed by an intramolecular cyclocondensation to yield 1,2,4,3,5-dithiaazadiborolidines (2) and by an intermolecular cyclocondensation to give the six-membered 1,3,5,2,4,6-thiadiazatriborines (3) and borazines (4). The product distribution is influenced by steric and electronic effects of the amine.
    Notes: Primäre Amine reagieren mit 3,5-Dimethyl-1,2,4,3,5-trithiadiborolan (1) unter Ringöffnung und intramolekularer Cyclokondensation zu 1,2,4,3,5-Dithiaazadiborolidinen (2) bzw. intermolekular zu den sechsgliedrigen 1,3,5,2,4,6-Thiadiazatriborinen (3) und Borazinen (4). Die Produktverteilung wird von sterischen und elektronischen Effekten des Amins beeinflußt.
    Additional Material: 2 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 2607-2623 
    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, LXXXV Diorganyl(phosphinoamino)boranes: Synthesis, Structure, and AssociationThe preparation of (phosphinoamino)boranes by various methods is described, and the selective cleavage of (silylamino)phosphines by boron halides is shown to depend on the substituents at the boron atom. In case of the system (C6H5)2P—NCH3—Si(CH3)3/BCl3 borontrichloride adds to the P-atom in the first step followed by (CH3)3SiCl elimination which obeys a first order rate law. Most of the (phosphinoamino)boranes are monomeric at room temperature and in solution but (CH3)2P—NCH3—B(CH3)2 associates with BP coordination at low temperature. Rotation at the BN bond is strongly restricted mainly due to steric hindrance. In these cases a long range coupling 4JPNBCH is observed which can be explained by the π-bond model. Thermally the (phosphinoamino)boranes decompose with formation of borazine and phosphine derivatives.
    Notes: Zur Darstellung von (Phosphinoamino)boranen werden verschiedene Verfahren beschrieben, wobei u. a. gezeigt wird, daß (Silylamino)phosphine durch Borhalogenide in Abhängigkeit von den Substituenten am Boratom selektiv gespalten werden. Im Falle des Systems(C6H5)2P—NCH3—Si(CH3)3/BCl3 wird im 1. Schritt Borchlorid am P-Atom addiert, dann schließt sich eine (CH3)3SiCl-Eliminierung an, die einem Geschwindigkeitsgesetz 1. Ordnung gehorcht. Die meisten (Phosphinoamino)borane sind bei Raumtemperatur und in Lösung monomer, jedoch assoziiert z. B. (CH3)2P—NCH3—B(CH3)2 unter BP-Koordination in der Kälte. Die Rotation um die BN-Bindung ist (hauptsächlich aus sterischen Gründen) stark gehindert. In diesen Fällen beobachtet man eine Fernkopplung 4JPNBCH′, die mit Hilfe des π-Bindungsmodells interpretiert wird. Die (Phosphinoamino)borane zersetzen sich thermisch in Borazine und Phosphinderivate.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 2774-2782 
    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, XIII. 35Cl NMR Data of Chloroboranes and Carboxylic Acid ChloridesChemical shifts Δ35Cl of chloroboranes of the type Cl3-nBXn (n = 0, 1, 2; X = alkyl, vinyl, phenyl, NR2, OR, SR) as well as of B2Cl4 and [(CH3)2N]2B2Cl2 can be interpreted by assuming a bond order 〉 1 between boron and chlorine. A comparison with δ35Cl of carboxylic acid chlorides Cl—C(Y)X (Y = O, S, NR; X = Cl, alkyl, NR2, OR, C(O)Cl) also indicates (pp)-π-interactions for these compounds. There exists a linear relationship between δ35Cl of chloroboranes and the calculated (CNDO/S) p-electron density qClp. δ35Cl- and δ19F data of corresponding compounds are compared.
    Notes: Chemische Verschiebungen Δ35Cl für Chlorborane des Typs Cl3-nBXn (n = 0, 1, 2; X = Alkyl, Vinyl, Phenyl, NR2, OR, SR) sowie für B2Cl4 und [(CH3)2N]2B2Cl2 lassen sich im Sinne einer Bindungsordnung 〉 1 zwischen Bor und Chlor interpretieren. Ein Vergleich mit δ35Cl von Carbonsäurechloriden Cl—C(Y)X (Y = O, S, NR, X = Cl, Alkyl, NR2, OR, C(O)Cl) läßt auch für diese Verbindungen den Schluß auf (pp)-π-Wechselwirkungen zu. Es besteht eine lineare Beziehung zwischen δ35Cl von Chlorboranen und der berechneten (CNDO/S) p-Elektronendichte qClp. δ35Cl und δ19F in analogen Verbindungen werden miteinander verglichen.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 2783-2789 
    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, LXXXVI. Phenyl-substituted Diborylamines[(C6H5)2B]2NH results not only by SiN-cleavage of hexamethyldisilazane with (C6H5)2 BBr but also by an exchange process from (C5H5)2B—NH—Si(CH3)3 or (C6H5)2B—NH—B(CH3)2. In contrast, (C6H5)2B—NCH3—Si(CH3)3is quite stable. At ≈ 50°C (C6H5)2B—NCH3—B(CH3)2 decomposes with phenyl group migration to yield dimethylphenylborane and the borazine 5.
    Notes: [(C6H5)2B]2NH entsteht nicht nur durch SiN-Spaltung von Hexamethyldisilazan mit (C6H5)2 BBr, sondern auch in einem Umordnungsprozeß aus (C6H5)2B—NH—Si(CH3)3 oder (C6H5)2B—NH—B(CH3)2. Im Gegensatz dazu ist (C6H5)2B—NCH3—Si(CH3)3stabil. (C6H5)2B—NCH3—B(CH3)2 zersetzt sich bei ≈ 50°C unter Phenylgruppenwanderung in Dimethylphenylboran und das Borazin 5.
    Additional Material: 1 Tab.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 2790-2801 
    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, LXXXVII. B,Si-Functional (Silylamino)boranes: a Contribution to the SiN-Cleavage by Boron Halides(Silylamino)boranes are virtually inert towards transsilylation or BN-cleavage by chloromethylsilanes. However, B- and/or Si-halogenated (silylamino)boranes are easily obtained from Si-halogenated disilazanes and boron halides, and, especially, from nonamethylcyclotrisilazane 14 and boron halides. Information concerning the degradation of this ring system have been obtained from several intermediates formed in the reaction of 14 with (CH3)2BBr.
    Notes: (Silylamino)borane sind weitgehend inert gegenüber einer Umsilylierung bzw. BN-Spaltung durch Chlormethylsilane. Hingegen erhält man B- und/oder Si-halogenierte (Silylamino)borane aus Si-halogenierten Disilazanen und Borhalogeniden oder besonders einfach aus Nonamethylcyclotrisilazan 14 und Borhalogeniden. Verschiedene Zwischenprodukte, die bei der Reaktion von 14 und (CH3)2BBr gebildet werden, geben Hinweise auf den Abbau dieses Ringsystems.
    Additional Material: 2 Tab.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 1636-1642 
    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, LXXIX. Tris(diorganylboryl)aminesStepwise Sn  -  N cleavage of tris(triorganylstannyl)amines by bromodiorganylboranes finally leads to tris(diorganylboryl)amines (4-6) via [(triorganylstannyl)amino]boranes. According to n. m. r. data this new class of compounds possesses R2B groups of low π-charge densities at the boron atoms.
    Notes: Die schrittweise Sn  -  N-Spaltung an Tris(triorganylstannyl)aminen durch Diorganylborbromide führt über [(Triorganylstannyl)amino]borane zu Tris(diorganylboryl)aminen (4-6). Die Kernresonanzdaten der neuen Verbindungsklasse weisen auf R2B-Gruppierungen mit geringer π-Elektronendichte an den Boratomen hin.
    Additional Material: 1 Ill.
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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
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 2158-2167 
    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, LXXXIV. Derivatives of 1,2,4,5-Tetramethyl-1,2,4,3,5-triazadiborolidineThe synthesis of a series of triazadiborolidines of type B (2a-g) is described. Compounds with X = H, SCH3, or N(CH3)2 are stable, the alkoxy derivatives decompose with formation of B(OR)3 and the halogen derivatives (X = Cl, Br) are in equilibrium with their symmetrical counterparts A and C. Substituent effects are discussed on the basis of the n. m. r. spectra. They suggest a twisted five-membered ring for 2d, e and f.
    Notes: Es wird die Synthese einer Reihe von Triazadiborolidin-Derivaten B (2a-g) beschrieben. Verbindungen mit X = H, SCH3 und N(CH3)2 sind stabil, die Alkoxyderivate zersetzen sich unter B(OR)3-Bildung und die Halogenderivate (X = Cl, Br) äquilibrieren mit ihren symmetrischen Gegenstücken A und C. Anhand der NMR-Spektren werden die Substituenteneffekte diskutiert. Sie legen für 2d, e und f eine Verdrillung des Fünfringes nahe.
    Additional Material: 1 Ill.
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