A new approach to lithium-heavier alkali metal interchange reactions: synthesis of a tetralithium pentasodium mixed alkoxide-amide dome-shaped cage compound with an encapsulated hydroxide molecule

Kennedy, A.R. and MacLellan, J.G. and Mulvey, R.E. and Robertson, A. (2000) A new approach to lithium-heavier alkali metal interchange reactions: synthesis of a tetralithium pentasodium mixed alkoxide-amide dome-shaped cage compound with an encapsulated hydroxide molecule. Journal of the Chemical Society, Dalton Transactions, 2000 (22). pp. 4112-4116. ISSN 0300-9246 (http://dx.doi.org/10.1039/b006990f)

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Abstract

An investigation of metal-metal interchange reactions between alkali metal amides and alkali metal alkoxides, relevant to the area of superbases, has uncovered a novel adduct containing both components, which has been isolated from solution and crystallographically characterised. Formulated as [Li4Na4(ButO)4{PhN(H)}4(NaOH)(4-Me-py)4], this tetralithium pentasodium mixed alkoxide-amide can be synthesized either by reaction of lithium anilide with sodium t-butoxide or of sodium anilide with lithium t-butoxide, in the presence of the co-ordinating solvent 4-methylpyridine (4-Me-py). The single sodium hydroxide molecule in the formulation occurs adventitiously, but consistently. X-Ray crystallographic studies reveal a 17-vertex dome-shaped structure founded on a (NaN)4 basal ring, above which lies a smaller (LiO)4 ring then an apical Na atom: the OH- ion occupies an internal position within the dome. Discussion focuses on the striking resemblance between this structure and that of the previously reported tetralithium pentapotassium mixed alkoxide-enolate [Li4K4(ButO)4(C6H11O)4(KOH)(THF)5], and it is pointed out that the dominant factor in their common architectural design appears to be the encapsulated hydroxide molecule.

ORCID iDs

Kennedy, A.R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, MacLellan, J.G., Mulvey, R.E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564 and Robertson, A.;
  • Item type:Article
    ID code:1271
    Dates:
    Date
    Event
    27 October 2000
    Published
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user:Users 45 not found.
    Date deposited:23 Jun 2006
    Last modified:11 Nov 2024 08:15
    URI:https://strathprints.strath.ac.uk/id/eprint/1271
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