The first trimetallic lithium-sodium-potassium complex: Synthesis and crystal structure of a twelve-vertex Li2Na2K2N4O2 cage molecule containing an amide-alkoxide combination

F.M. Mackenzie, Robert Mulvey, W. Clegg, Lynne Horsburgh

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Abstract

Several molecular complexes containing a mixture of two alkali metals (e.g., lithium−sodium and lithium−potassium) have been characterised by X-ray crystallographic studies over the past decade.1 Here, in this paper, we break new ground in this important area of intermetallic chemistry by reporting the successful synthesis and X-ray crystallographic characterization of an unprecedented trimetallic (lithium−sodium−potassium) formulation. Furthermore, the new complex, [{[PhN(H)]2(t-BuO)LiNaK·(TMEDA)2}2], (1), is closely related to the cocompositions currently employed as “superbases”,2 reagents of boosted deprotonating ability, in organic synthesis. Two recently reported crystal structures regarded to be architectural models for superbases, a carbanion−alkoxide3a and a carbanion−amide3b combination, both contain their two anionic functionalities (C-/RO- and C-/R2N-, respectively) within one ligand. On the other hand, more realistically, 1 contains two distinct types of anionic ligand [amide−alkoxide (R2N-/RO-)]4 as is the case in superbase reagents.2
LanguageEnglish
Pages4721-4722
Number of pages2
JournalJournal of the American Chemical Society
Volume118
Issue number19
DOIs
Publication statusPublished - 15 May 1996

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Lithium
Amides
Potassium
Crystal structure
Sodium
Molecules
Ligands
X-Rays
Alkali Metals
Synthetic Chemistry Techniques
X rays
Alkali metals
Intermetallics

Keywords

  • tert butoxide
  • stack
  • alkali metals

Cite this

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title = "The first trimetallic lithium-sodium-potassium complex: Synthesis and crystal structure of a twelve-vertex Li2Na2K2N4O2 cage molecule containing an amide-alkoxide combination",
abstract = "Several molecular complexes containing a mixture of two alkali metals (e.g., lithium−sodium and lithium−potassium) have been characterised by X-ray crystallographic studies over the past decade.1 Here, in this paper, we break new ground in this important area of intermetallic chemistry by reporting the successful synthesis and X-ray crystallographic characterization of an unprecedented trimetallic (lithium−sodium−potassium) formulation. Furthermore, the new complex, [{[PhN(H)]2(t-BuO)LiNaK·(TMEDA)2}2], (1), is closely related to the cocompositions currently employed as “superbases”,2 reagents of boosted deprotonating ability, in organic synthesis. Two recently reported crystal structures regarded to be architectural models for superbases, a carbanion−alkoxide3a and a carbanion−amide3b combination, both contain their two anionic functionalities (C-/RO- and C-/R2N-, respectively) within one ligand. On the other hand, more realistically, 1 contains two distinct types of anionic ligand [amide−alkoxide (R2N-/RO-)]4 as is the case in superbase reagents.2",
keywords = "tert butoxide, stack, alkali metals",
author = "F.M. Mackenzie and Robert Mulvey and W. Clegg and Lynne Horsburgh",
year = "1996",
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T1 - The first trimetallic lithium-sodium-potassium complex

T2 - Journal of the American Chemical Society

AU - Mackenzie, F.M.

AU - Mulvey, Robert

AU - Clegg, W.

AU - Horsburgh, Lynne

PY - 1996/5/15

Y1 - 1996/5/15

N2 - Several molecular complexes containing a mixture of two alkali metals (e.g., lithium−sodium and lithium−potassium) have been characterised by X-ray crystallographic studies over the past decade.1 Here, in this paper, we break new ground in this important area of intermetallic chemistry by reporting the successful synthesis and X-ray crystallographic characterization of an unprecedented trimetallic (lithium−sodium−potassium) formulation. Furthermore, the new complex, [{[PhN(H)]2(t-BuO)LiNaK·(TMEDA)2}2], (1), is closely related to the cocompositions currently employed as “superbases”,2 reagents of boosted deprotonating ability, in organic synthesis. Two recently reported crystal structures regarded to be architectural models for superbases, a carbanion−alkoxide3a and a carbanion−amide3b combination, both contain their two anionic functionalities (C-/RO- and C-/R2N-, respectively) within one ligand. On the other hand, more realistically, 1 contains two distinct types of anionic ligand [amide−alkoxide (R2N-/RO-)]4 as is the case in superbase reagents.2

AB - Several molecular complexes containing a mixture of two alkali metals (e.g., lithium−sodium and lithium−potassium) have been characterised by X-ray crystallographic studies over the past decade.1 Here, in this paper, we break new ground in this important area of intermetallic chemistry by reporting the successful synthesis and X-ray crystallographic characterization of an unprecedented trimetallic (lithium−sodium−potassium) formulation. Furthermore, the new complex, [{[PhN(H)]2(t-BuO)LiNaK·(TMEDA)2}2], (1), is closely related to the cocompositions currently employed as “superbases”,2 reagents of boosted deprotonating ability, in organic synthesis. Two recently reported crystal structures regarded to be architectural models for superbases, a carbanion−alkoxide3a and a carbanion−amide3b combination, both contain their two anionic functionalities (C-/RO- and C-/R2N-, respectively) within one ligand. On the other hand, more realistically, 1 contains two distinct types of anionic ligand [amide−alkoxide (R2N-/RO-)]4 as is the case in superbase reagents.2

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