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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

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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.

Item type: Article
ID code: 1271
Keywords: alkali metal amides, alkali metal alkoxides, crystallographically, sodium anilide, X-Ray, hydroxide molecule, Chemistry
Subjects: Science > Chemistry
Department: Faculty of Science > Pure and Applied Chemistry
Related URLs:
    Depositing user: Catriona Mccallum
    Date Deposited: 23 Jun 2006
    Last modified: 12 Mar 2012 10:36
    URI: http://strathprints.strath.ac.uk/id/eprint/1271

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