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  • 1
    ISSN: 1434-1948
    Keywords: Cluster ; Nickel ; Tin ; Bimetallic complexes ; Electrochemistry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Addition of stannylene [{(SiMe3)2CH}2Sn:] (2) to the unbridged homobimetallic Ni-Ni bond of [{PEt3Ni(η5-Cp)}2] (1) gives the heterobimetallic, tetranuclear compound [{{(SiMe3)2CH}2Sn-Ni(η5-Cp)}2] (3) with a butterfly arrangement and leaves the Ni-Ni bond of 1 intact. Elimination of both PEt3 ligands from the starting material 1 is observed, probably due to steric restraints. Compound 3 is formally related to the hypothetical closo-borane B4H42-. The Ni-Ni bond in 3 is only slightly elongated [2.454(3) Å] when compared to the starting material 1 [2.41(1) Å]. Compound 3 displays a butterfly arrangement with a hinge angle of 62.5°. An alternative route to 3 is by a direct reaction between nickelocene (5) and Lappert's stannylene [{(SiMe3)2CH}2Sn:] in 63% yield. Treating 3 with water results in the cleavage of an Ni-Sn bond and subsequent opening of the cluster cage of 3 to form the trinuclear compound [(η5-Cp)Ni{Sn(CH(SiMe3)2}2OH] (6) having an Sn-OH-Sn bridge. The hydroxy proton in 6 can be exchanged by deuterium within a few minutes, as determined by 1H-NMR spectroscopy, giving the monodeuterio product, [D1]-6. Compound 6 is reactive towards acetonitrile, leading to cleavage of one Ni-Sn bond, elimination of one [{(SiMe3)2CH}2Sn:] unit, and formation of the organotin hydroxo complex [{(SiMe3)2CH}2(OH)Sn-Ni(η5-Cp)(CH3CN)] (7). In this complex, acetonitrile is coordinated to Ni via its σ lone pair, bearing the OH ligand in a terminal bonding mode to tin.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 491-497 
    ISSN: 1434-1948
    Keywords: Boron ; Diazaboroles ; Hydrides ; Tin ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1,3-Di-tert-butyl-2,3-dihydro-1H-1,3,2-diazaborole (4a) and 1,3-bis(2,6-dimethylphenyl)-2,3-dihydro-1H-1,3,2-diazaborole (4b) were formed by the reaction of the corresponding 2-bromo or 2-iodo derivatives 1a and 2b with LiAlH4. Treatment of 1a with n-butyllithium afforded 2-n-butyl-1,3-di-tert-butyl-2,3-dihydro-1H-1,3,2-diazaborole (5a), whereas 1,3-di-tert-butyl-2-cyano-2,3-dihydro-1H-1,3,2-diazaborole (3a) was converted into the 2-tert-butyl derivative 6a or the 2-ethynyl-1,3,2-diazaborole 7a by means of tert-butyllithium or by the ethylenediamine adduct of lithium acetylide. Similarly, 1,3-di-tert-butyl-2-trimethylstannyl-2,3-dihydro-1H-1,3,2-diazaborole (8a) and 1,3-bis(2,6-dimethylphenyl)-2-trimethylstannyl-2,3-dihydro-1H-1,3,2-diazaborole (8b) were accessible from 1a or 2b and trimethylstannyllithium. In the complex 9a the compound 3a serves as an η1 ligand towards the [Cr(CO)5] unit via the cyano group. These novel compounds were characterized by 1H-, 11B-, 13C-, and 119Sn-NMR spectroscopy, as well as by X-ray structure analyses of 4b, 8a, and 9a.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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