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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: Azaborolinyl Complexes, X1). Synthesis and Properties of (1-tert-Butyl-2-methyl-η-1,2-azaborolinyl)carbonylmanganese and-molybdenum Complexes1-tert-Butyl-2-methyl-1,2-azaborolinyllithium (1) reacts with [CH3CN)3Mn(CO)3]PF6 to give (1-tert-butyl-2-methyl-η-1,2-azaborolinyl)tricarbonylmanganese (2). Neutral 1-tert-butyl-2-methyl-1,2-azaboroline (3) and Mo(CO)6 form π-ally(1-tert-butyl-2-methyl-η-1,2-azaborolinyl)-dicarbonylmolybdenum (4). The formation of the allyl group is due to the decomposition of an azaborolinyl ring under the reaction conditions. 2 and 4 are characterized by mass, IR, and NMR spectra. 4 could be investigated by X-ray analysis. Orthorhombic, space group Pbca, Z = 8, a = 1697.4(9), b = 1441.8(5), c = 1219.4(7) pm. The chirality of the azaborolinyl ring causes the formation of enantiomers which exist as a racemate in the crystal.
    Notes: 1-tert-Butyl-2-methyl-1,2-azaborolinyllithium (1) reagiert mit [(CH3CN)3Mn(CO)3]PF6 zum (1-tert-Butyl-2-methyl-η-1,2-azaborolinyl)tricarbonylmangan (2). Neutrales 1-tert-Butyl-2-methyl-1,2-azaborolin (3) und Mo(CO)6 bilden π-Allyl(1-tert-butyl-2-methyl-η-1,2-azaborolinyl)-dicarbonylmolybdän (4). Die Bildung der Allygruppe ist auf den Zerfall eines Azaborolin-Ringes unter den Reaktionsbedingungen zurückzuführen. 2 und 4 werden durch Massen-, IR- und NMR-Spektren charakterisiert. Von 4 konnte eine Röntgenstrukturanalyse durchgeführt werden: orthorhombisch, Raumgruppe Pbca, Z = 8, a = 1697.4(9), b = 1441.8(5), c = 1219.4(7) pm. Die Chiralität des Azaborolinyl-Ringes bedingt die Bildung von Enantiomeren, die im Kristall als Racemat vorliegen.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1052-1060 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Azaborolinyl Complexes, XIII. Synthesis and Properties of Bis(1-tert-butyl-2-methyl-η3-1,2-azaborolinyl)nickelThe reaction of 1-tert-butyl-2-methyl-1,2-azaborolinyllithium (1) with NiBr2 leads to the sandwich complex bis(1-tert-butyl-2-methyl-η3-1,2-azaborolinyl)nickel (2). For the first time it is noticed that the azaborolinyl ring does not serve as η5 but as η3 ligand. The 1H NMR spectrum shows the existence of two isomers (2a,b), one of them could be investigated by X-ray analysis. As a result only the three ring carbon atoms possess binding distances to the nickel atom, whereas boron and nitrogen do not show any covalent interactions with the metal. The position of the signals of the ring protons in the 1H NMR spectrum differs characteristically from the position in other azaborolinyl sandwich complexes and in π-allyl compounds.
    Notes: Die Reaktion von 1-tert-Butyl-2-methyl-1,2-azaborolinyllithium (1) mit NiBr2 führt zum Sandwichkomplex Bis(1-tert-butyl-2-methyl-η3-1,2-azaborolinyl)nickel (2). Erstmals wird beobachtet, daβ der Azaborolinyl-Ring nicht als η5-, sondern als η3-Ligand dient. Das 1H-NMR-Spektrum zeigt das Vorliegen von zwei Isomeren (2a,b), von denen eines röntgenstrukturanalytisch untersucht werden konnte. Danach haben nur die drei Ringkohlenstoffe bindende Abstände zum Nickelatom, während Bor und Stickstoff keine kovalenten Wechselwirkungen mit dem Metall zeigen. Die Lage der Ringprotonen-Signale im 1H-NMR-Spektrum weicht charakteristisch von der Lage in anderen Azaborolinyl-Sandwichkomplexen und in π-Allylverbindungen ab.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Azaborolinyl Complexes, VII. Preparative and Structural Studies on η-1,2-Azaborolinyl Complexes of Titanium, Vanadium, Iron, and Cobalt1-tert-Butyl-2-methyl-1,2-azaborolinyllithium reacts with FeBr2 and CoBr2 to give the sandwich complexes bis(1-tert-butyl-2-methyl-η-1,2-azaborolinyl)iron (3) and -cobalt (4), respectively. With TiBr4 bis(1-tert-butyl-2-methyl-η-1,2-azaborolinyl)titanium dibromide (5) can be isolated. The sandwich complex bis[2-methyl-1-(trimethylsilyl)-η-1,2-azaborolinyl]vanadium (6) is formed from neutral 2-methyl-1-(trimethylsilyl)-Δ3-1,2-azaboroline and vanadium atoms at - 130°C/10-4torr. By means of NMR and X-ray investigations, it an be shown that the recently synthesized sandwich compounds bis[2-methyl-1-(trimethylsilyl)-η-1,2-azaborolinyl]iron (1) and -cobalt (2) as well as 3 each from 2 isomers which are to be described as clockwise (1a, 2a, 3a) and anti-clockwise conformations (1b, 2b, 3b), respectively. The same conditions are assumed for 4, 5, and 6. The staggered isomer 6 has also been characterized by X-ray diffraction methods.
    Notes: 1-tert-Butyl-1,2-azaborolinyllithium reagiert mit FeBr2 und CoBr2 zu den Sandwichkomplexen Bis(1-tert-butyl-2-methyl-η-1,2-azaborolinyl)eisen (3) und -cobalt (4). Mit TiBr4 erhält man Bis(1-tert-butyl-2-methyl-η-1,2-azaborolinyl)titan-dibromid (5). Der Sandwichkomplex Bis-[2-methyl-1-(trimethylsilyl)-η-1,2-azaborolinyl]vanadin (6) bildet sich aus neutralem 2-Methyl-1-(trimethylsilyl)-Δ3-1,2-azaborolin und Vanadinatomen bei -130°C/10-4 Torr. Anhand von NMR- und Röntgenstrukturuntersuchungen kann gezeigt werden, daß die kürzlich dargestellten Sandwichverbindungen Bis[2-methyl-1-(trimethylsilyl)-η-1,2-azaborolinyl]eisen (1) und -cobalt (2) ebenso wie 3 je 2 Isomere bilden, die als gleichläufige (1a, 2a, 3a) bzw. gegenläufige Konformationen (1b, 2b, 3b) zu beschreiben sind. Gleiche Verhältnisse werden für 4, 5 und 6 angenommen. Das Isomere 6 wurde ebenfalls durch Röntgenstrukturanalyse charakterisiert.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 115 (1982), S. 732-737 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Azaborolinyl Complexes, VI. Synthesis and Properties of the 1,2-Azaborolinyl Anion2-Methyl-1-(trimethylsilyl)-Δ3-1,2-azaboroline (1) reacts with lithium 2,2,6,6-tetramethylpiperidide [Li(TMP)] to give the lithium salt 2 of the 2-methyl-1-(trimethylsilyl)-1,2-azaborolinyl anion. Results of quantum chemical calculations with MNDO methods for the unsubstituted azaborolinyl anion as well as for the neutral azaboroline allow comparisons with data determined by X-ray investigation. 1 reacts with FeBr2 and CoBr2 to yield the sandwich complexes bis[2-methyl-1-(trimethylsilyl)-1,2-azaborolinyl]iron (3) and -cobalt (4), respectively. The molecular structure of 4 has been determined by single-crystal X-ray diffraction methods.
    Notes: 2-Methyl-1-(trimethylsilyl)-Δ3-1,2-azaborolin (1) reagiert mit Lithium-2,2,6,6-tetramethylpiperidid [Li(TMP)] zum Lithiumsalz 2 des 2-Methyl-1-(trimethylsilyl)-1,2-azaborolinyl-Anions. Die Ergebnisse quantenchemischer Rechnungen nach der MNDO-Methode am unsubstituierten Azaborolinyl-Anion sowie am neutralen Azaborolin erlauben Vergleiche mit röntgenstrukturanalytisch ermittelten Daten. 1 reagiert mit FeBr2 und CoBr2 zu den Sandwichkomplexen Bis[2-methyl-1-(trimethylsilyl)-1,2-azaborolinyl]eisen (3) und -cobalt (4). Die Molekülstruktur von 4 wurde mittels Einkristall-Röntgenbeugungsmethoden bestimmt.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 951-959 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Azaborolinyl Complexes, VIII. Chemical and Spectroscopic Investigations on Bis(η-1,2-azaborolinyl)iron ComplexesBis[2-methyl-1-(trimethylsilyl)-η-1,2-azaborolinyl]iron (1) is lithiated at the nitrogen atom by lithium 2,2,6,6-tetramethylpiperidide [Li(TMP)] with elimination of the Si(CH3)3 groups. With tert-butyl alcohol bis(2-methyl-η-1,2-azaborolinyl)iron (2) is formed which has been investigated by an X-ray analysis. It confirms the same clockwise and staggered conformation as in the starting isomer of 1, namely 1a. If a mixture of isomers with clockwise and anti clockwise azaborolinyl rings (1a and b) is applied for lithiation and a methylation is carried out with CH3I, bis(1,2-dimethyl-η-1,2-azaborolinyl)iron (4) is formed as a mixture of isomers (4a and b). 4 may also be synthesized via the methylated ring 6 and FeBr2. Lithiation of 1a and following ethylation with C2H5Br leads to bis(1-ethyl-2-methyl-η-1,2-azaborolinyl)iron (5), again as a pure clockwise isomer.
    Notes: Bis[2-methyl-1-(trimethylsilyl)-η-1,2-azaborolinyl]eisen (1) wird durch Lithium-2,2,6,6-tetramethylpiperidid [Li(TMP)] am Stickstoffatom unter Abspaltung der Si(CH3)3-Gruppen lithiiert. Mit tert-Butylalkohol entsteht daraus Bis(2-methyl-η-1,2-azaborolinyl)eisen (2). Eine Röntgenstrukturanalyse von 2 bestätigt dieselbe gleichläufige und gestaffelte Konformation wie beim Ausgangsisomeren von 1, nämlich 1a. Verwendet man zur Lithiierung ein Isomerengemisch mit gleich- und gegenläufigen Azaborolinylringen (1a und b) und methyliert mit CH3I, so bildet sich Bis(1,2-dimethyl-η-1,2-azaborolinyl)eisen (4) als Isomerengemisch (4a und b). 4 kann auch direkt über den methylierten Ring 6 und FeBr2 hergestellt werden. Die Lithiierung von 1a und anschließende Ethylierung mit C2H5Br führt zu Bis(1-ethyl-2-methyl-η-1,2-azaborolinyl)eisen (5), wiederum als reines, gleichläufiges Isomeres.
    Additional Material: 1 Ill.
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  • 6
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No Abstract.Das vollständige Manuskript dieser Zuschrift erscheint in: Angew. Chem. Suppl. 1982, 50.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0570-0833
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No Abstract.The complete manuscript of this communication appears in: Angew. Chem. Suppl. 1982, 50. DOI:10.1002/anie.198200500
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 0570-0833
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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