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: https://orcid.org/0000-0002-3998-7506, Honeyman, Gordon W., Kennedy, Alan R. ORCID: https://orcid.org/0000-0003-3652-6015, Mulvey, Robert E. ORCID: https://orcid.org/0000-0002-1015-2564, Ramsay, Donna L. and Robertson, Stuart D. ORCID: https://orcid.org/0000-0002-9330-8770;-
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Item type: Article ID code: 51790 Dates: DateEvent2015Published4 February 2015Published Online28 January 2015AcceptedSubjects: Science > Chemistry Department: Faculty of Science > Pure and Applied Chemistry Depositing user: Pure Administrator Date deposited: 19 Feb 2015 13:32 Last modified: 27 Sep 2024 00:50 URI: https://strathprints.strath.ac.uk/id/eprint/51790