Structurally defined zincated and aluminated complexes of ferrocene made by alkali-metal-synergistic syntheses

Clegg, William and Crosbie, Elaine and Dale-Black, Sophie H. and Hevia, Eva and Honeyman, Gordon W. and Kennedy, Alan R. and Mulvey, Robert E. and Ramsay, Donna L. and Robertson, Stuart D. (2015) Structurally defined zincated and aluminated complexes of ferrocene made by alkali-metal-synergistic syntheses. Organometallics, 34 (11). pp. 2580-2589. ISSN 0276-7333 (https://doi.org/10.1021/om5012352)

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Abstract

Reaction of ferrocene with 1 or 2 molar equiv of the synergistic-operative bimetallic sodium zincate base TMEDA·Na(μ-TMP)(μ-tBu)Zn(tBu) yields mainly mono- or dizincated complexes TMEDA·Na(μ-TMP)[μ-(C5H4)Fe(C5H5)]ZntBu (1) and [TMEDA·Na(μ-TMP)Zn(tBu)]2(C5H4)2Fe (2). Likewise, the separated pairing of Li(TMP) and (TMP)AliBu2 in the presence of THF can mono- or dimetalate ferrocene in a synergistic two-step lithiation/trans-metal-trapping protocol to give THF·Li(μ-TMP)[μ-(C5H4)Fe(C5H5)]Al(iBu)2 (4) or [THF·Li(μ-TMP)Al(iBu)2]2(C5H4)2Fe (5). In the absence of Lewis donating cosolvents, a 4-fold excess of the sodium zincate appears to produce an unprecedented 4-fold zincated ferrocene of formula Na4(TMP)4Zn4(tBu)4[(C5H3)2Fe] (3), whereas when donor solvent is withheld from the lithium/aluminum pairing, only dimetalation of ferrocene is possible. Tetrametalation seems to be inhibited by the in situ generation of TMP(H) via amido basicity, which then acts as a Lewis donor toward lithium, preventing inverse-crown formation and preferentially forming the Lewis acid–Lewis base adduct [TMP(H)·Li(μ-TMP)Al(iBu)2]2(C5H4)2Fe (6). With the exception of 3, all aforementioned complexes have been characterized by X-ray crystallography, while 1–6 have also been studied by solution NMR spectroscopic studies.

ORCID iDs

Clegg, William, Crosbie, Elaine, Dale-Black, Sophie H., Hevia, Eva ORCID logoORCID: https://orcid.org/0000-0002-3998-7506, Honeyman, Gordon W., Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564, Ramsay, Donna L. and Robertson, Stuart D. ORCID logoORCID: https://orcid.org/0000-0002-9330-8770;
  • Item type:Article
    ID code:51790
    Dates:
    Date
    Event
    2015
    Published
    4 February 2015
    Published Online
    28 January 2015
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:19 Feb 2015 13:32
    Last modified:11 Nov 2024 10:58
    URI:https://strathprints.strath.ac.uk/id/eprint/51790
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