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

A.R. Kennedy, J.G. MacLellan, R.E. Mulvey, A. Robertson

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27 Citations (Scopus)

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.
LanguageEnglish
Pages4112-4116
Number of pages4
JournalJournal of the Chemical Society, Dalton Transactions
Volume2000
Issue number22
DOIs
Publication statusPublished - 27 Oct 2000

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Anilides
Alkali Metals
Domes
Interchanges
Lithium
Amides
Heavy metals
Metals
Sodium
Sodium Hydroxide
Molecules
Architectural design
Ions
X rays
Atoms
hydroxide ion

Keywords

  • alkali metal amides
  • alkali metal alkoxides
  • crystallographically
  • sodium anilide
  • X-Ray
  • hydroxide molecule

Cite this

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title = "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",
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.",
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author = "A.R. Kennedy and J.G. MacLellan and R.E. Mulvey and A. Robertson",
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T1 - 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

AU - Kennedy, A.R.

AU - MacLellan, J.G.

AU - Mulvey, R.E.

AU - Robertson, A.

PY - 2000/10/27

Y1 - 2000/10/27

N2 - 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.

AB - 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.

KW - alkali metal amides

KW - alkali metal alkoxides

KW - crystallographically

KW - sodium anilide

KW - X-Ray

KW - hydroxide molecule

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DO - 10.1039/b006990f

M3 - Article

VL - 2000

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JO - Journal of the Chemical Society, Dalton Transactions

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JF - Journal of the Chemical Society, Dalton Transactions

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