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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1-5 
    ISSN: 1434-1948
    Keywords: Terpyridine ligands ; Ferrocenes ; Iron ; Ruthenium ; Cyclic voltammetry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2,2′:6′,2′′-Terpyridines bearing a substituent × in the 4′-position [3a: × = Fc-C≡C-p-C6H4; 3b: × = Fc#-C≡C-p-C6H4; Fc = (C5H5)Fe(C5H4), Fc# = (C5Me4H)Fe(C5Me4)] were prepared by Pd0-catalysed cross-coupling reactions. 3b was characterised by X-ray structure analysis. [(3a)RuCl2(DMSO)] (4a) and [(3b)RuCl2(DMSO)] (4b) were obtained by reaction of [RuCl2(DMSO)4] with 1 equivalent of 3a and 3b, respectively, while the analogous reaction with 2 equivalents afforded [(3a)2Ru][PF6]2 (5a) and [(3b)2Ru][PF6]2 (5b), respectively, after precipitation with aqueous [NH4][PF6]. Similarly, [(3a)Ru(tpy)][PF6]2 (6) was isolated from the reaction of 4a with 2,2′:6′,2′′-terpyridine (tpy). Compounds 3 and 5 were investigated by cyclic voltammetry, which revealed that the introduction of eight methyl groups leads to the expected cathodic shift of the E0′ values of ca. 0.44 V for the ferrocenyl-centered redox processes.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    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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