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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 2691-2699 
    ISSN: 0009-2940
    Keywords: Hydroboration ; Tetraborane(8) ; μ-(tert-butylimino)-μ-(tetramethylpiperidino)- ; arachno-Undecaboranates(13), 11-(organylamino)-11-(tetramethylpiperidinio)- ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Contributions to the Chemistry of Boron, 213[1]. - Reactions of an Amino-imino-borane with Triborane(7) and Decaborane(14)Triborane(7)-THF hydroborates (tert-butylimino)(tetramethylpiperidino)borane 1 slowly to form μ-(tert-butylamino)-μ-(tetramethylpiperidino)tetraborane(8) 5. This molecule shows fluxional behaviour at ambient temperature in solution. In the solid state, an X-ray structure analysis reveals the presence of the asymmetric 1104-styx valence tautomer. 1 does not react at ambient temperature with pentaborane(9) in dichloromethane/hexane solution. However, 1 reacts rapidly with decaborane(14) to produce a tetramethylpiperidine adduct of an 11-(tert-butylamino)undecaborane(14) as determined by an X-ray structure analysis. The same kind of reaction occurs between decaborane(14) and (2,6-diisopropylphenylimino)-(2,2,6,6-tetramethylpiperidino)borane. Thus, decaborane(14) acts as a diprotic acid towards amino-imino-boranes.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0009-2940
    Keywords: Borane, [(di-tert-butylphosphanyl)imino](2,2,6,6-tetramethylpiperidino) dimer ; Phosphonium, di-tert-butylmethyl[(2,2,6,6-tetramethylpiperidinoborylene)imino]iodide ; Haloboration ; Hydroboration ; Metal carbonyl complexes of [(di-tert-butylphosphanyl)imino](2,2,6,6-tetramethylpiperidino)borane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The elements oxygen, sulfur, and selenium add to the P atom of the title borane 1. In contrast to the formation of tmp—B≡N—P(X)tBu2 (X = S, Se), the P oxide (X = O) dimerizes to [tmp—B≡N—P(O)tBu2]2 (5) with an eight-membered flat boat-shaped B2N2P2O2 ring. Borane 1 reacts readily with Mel to yield a phosphonium salt 8 and with BBr3 to give an adduct 9 with a B—P bond. In contrast, bis(dichloroboryl)-methane not only adds to 1 to generate a coordinate B—P bond but also chloroborates the B≡N triple bond, the final product being a new five-membered heterocycle 10. Similarly, the BH3 component of BH3·SMe2 first adds to the P atom of 1 followed by reaction of a second mol of BH3·SMe2 which hydroborates the B≡N triple bond. Finally, metal carbonyl fragments add only to the P atom of 1, demonstrating also that the chemistry of the molecule 1 is dominated by the basicity of its P center.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 711-717 
    ISSN: 0009-2940
    Keywords: Alkynylboranes ; Borirenes ; Boraallenes ; Calculations, ab initio ; Hydroboration ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dimeric(dimethylamino)(phenylethynyl)borane (2)2 is formed by the reaction of bis(dimethylamino)(phenylethynyl)-borane (1) with 9-BBN-H. An X-ray single-crystal diffraction study revealed a central B2N2 four-membered ring for (2)2 with both alkynyl groups pointing to the same side in a cisoid arrangement. However, solution and solid-state NMR as well as ab initio calculations on model compounds show that the cis arrangement in the crystal chosen for X-ray diffraction is not representative of the bulk material, which consists of both cis and trans isomers. Further investigations of the competition between hydrogen-amino group exchange and hydroboration in the reaction of amino-alkynylboranes with hydroborating agents (9-BBN-H and catB-H) show the exchange to be much faster even in the presence of Wilkinson's catalyst and with cyclic amino-alkynylboranes such as 1,3-dimethyl-2-[(trimethylsily1)ethynyl]-1,3,2-diazaborolidine (3). Ab initio calculations on alkynylboranes I, borirenes II, and boraallenes III, which are all geometrical isomers, show alkynylboranes to be the most stable isomers only if strongly π-donating groups X (X = NH2, F) are attached to the boron atom. In any case, boraallenes are highest in energy.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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