A remarkable isostructural homologous series of mixed lithium-heavier alkali metal tert-butoxides [(t-BuO)(8)Li4M4] (M = Na, K, Rb or Cs)

D R Armstrong, W Clegg, A M Drummond, S T Liddle, Robert Mulvey

Research output: Contribution to journalArticle

38 Citations (Scopus)

Abstract

Three new mixed lithium-heavier alkali metal tert-butoxides [(t-BuO)(8)Li4M4] (M = Na, Rb, Cs) are reported which, added to the previously discovered potassium analogue [(t-BuO)(8)Li4K(4)], complete the homologous series. Remarkably, X-ray crystallographic studies reveal that all four heterometallic compounds adopt a common structure. This sixteen-vertex O8Li4M4 "breastplate" motif is built around novel (M+)(4) planes (M = Na, K, Rb, Cs), both bees of which support chelating (O4Li2)(2-) dianions. Each such dianion is positioned approximately normal with respect to the other. Bonding within the breastplate structure involves a combination of mu (3)-Li. mu (4)-M, mu (3)-O, and mu (4)-O centers. Ab initio MO calculations on model systems predict that formation of the heterometallic breastplate from the exclusively mu (3)-bonded frameworks of its component homometallic structures is a favorable exothermic process. Best regarded as an inherently stable contacted triple ion sandwich comprising a dianion-tetramonocation-dianion arrangement, the breastplate motif is likely to be more widely applicable within heterometallic structural chemistry than so far recognized. This point is discussed with reference to a previously documented series of heterometallic p-block metal-based imide structures of general formula [(CyN)(8)(M4M42)-M-1], where M-1 = Sb or As and M-2 = Ag, Cu, or Na.

LanguageEnglish
Pages11117-11124
Number of pages8
JournalJournal of the American Chemical Society
Volume122
Issue number45
DOIs
Publication statusPublished - 15 Nov 2000

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Imides
Alkali Metals
Bees
Alkali metals
Heavy Metals
Chelation
Lithium
Heavy metals
Potassium
Metals
X-Rays
Ions
X rays
ganhuangenin
potassium tert-butoxide

Keywords

  • molecular orbital methods
  • x-rays
  • crystal structures
  • basis sets
  • cage complex
  • potassium
  • ligands

Cite this

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title = "A remarkable isostructural homologous series of mixed lithium-heavier alkali metal tert-butoxides [(t-BuO)(8)Li4M4] (M = Na, K, Rb or Cs)",
abstract = "Three new mixed lithium-heavier alkali metal tert-butoxides [(t-BuO)(8)Li4M4] (M = Na, Rb, Cs) are reported which, added to the previously discovered potassium analogue [(t-BuO)(8)Li4K(4)], complete the homologous series. Remarkably, X-ray crystallographic studies reveal that all four heterometallic compounds adopt a common structure. This sixteen-vertex O8Li4M4 {"}breastplate{"} motif is built around novel (M+)(4) planes (M = Na, K, Rb, Cs), both bees of which support chelating (O4Li2)(2-) dianions. Each such dianion is positioned approximately normal with respect to the other. Bonding within the breastplate structure involves a combination of mu (3)-Li. mu (4)-M, mu (3)-O, and mu (4)-O centers. Ab initio MO calculations on model systems predict that formation of the heterometallic breastplate from the exclusively mu (3)-bonded frameworks of its component homometallic structures is a favorable exothermic process. Best regarded as an inherently stable contacted triple ion sandwich comprising a dianion-tetramonocation-dianion arrangement, the breastplate motif is likely to be more widely applicable within heterometallic structural chemistry than so far recognized. This point is discussed with reference to a previously documented series of heterometallic p-block metal-based imide structures of general formula [(CyN)(8)(M4M42)-M-1], where M-1 = Sb or As and M-2 = Ag, Cu, or Na.",
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month = "11",
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A remarkable isostructural homologous series of mixed lithium-heavier alkali metal tert-butoxides [(t-BuO)(8)Li4M4] (M = Na, K, Rb or Cs). / Armstrong, D R ; Clegg, W ; Drummond, A M ; Liddle, S T ; Mulvey, Robert.

In: Journal of the American Chemical Society, Vol. 122, No. 45, 15.11.2000, p. 11117-11124.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A remarkable isostructural homologous series of mixed lithium-heavier alkali metal tert-butoxides [(t-BuO)(8)Li4M4] (M = Na, K, Rb or Cs)

AU - Armstrong, D R

AU - Clegg, W

AU - Drummond, A M

AU - Liddle, S T

AU - Mulvey, Robert

PY - 2000/11/15

Y1 - 2000/11/15

N2 - Three new mixed lithium-heavier alkali metal tert-butoxides [(t-BuO)(8)Li4M4] (M = Na, Rb, Cs) are reported which, added to the previously discovered potassium analogue [(t-BuO)(8)Li4K(4)], complete the homologous series. Remarkably, X-ray crystallographic studies reveal that all four heterometallic compounds adopt a common structure. This sixteen-vertex O8Li4M4 "breastplate" motif is built around novel (M+)(4) planes (M = Na, K, Rb, Cs), both bees of which support chelating (O4Li2)(2-) dianions. Each such dianion is positioned approximately normal with respect to the other. Bonding within the breastplate structure involves a combination of mu (3)-Li. mu (4)-M, mu (3)-O, and mu (4)-O centers. Ab initio MO calculations on model systems predict that formation of the heterometallic breastplate from the exclusively mu (3)-bonded frameworks of its component homometallic structures is a favorable exothermic process. Best regarded as an inherently stable contacted triple ion sandwich comprising a dianion-tetramonocation-dianion arrangement, the breastplate motif is likely to be more widely applicable within heterometallic structural chemistry than so far recognized. This point is discussed with reference to a previously documented series of heterometallic p-block metal-based imide structures of general formula [(CyN)(8)(M4M42)-M-1], where M-1 = Sb or As and M-2 = Ag, Cu, or Na.

AB - Three new mixed lithium-heavier alkali metal tert-butoxides [(t-BuO)(8)Li4M4] (M = Na, Rb, Cs) are reported which, added to the previously discovered potassium analogue [(t-BuO)(8)Li4K(4)], complete the homologous series. Remarkably, X-ray crystallographic studies reveal that all four heterometallic compounds adopt a common structure. This sixteen-vertex O8Li4M4 "breastplate" motif is built around novel (M+)(4) planes (M = Na, K, Rb, Cs), both bees of which support chelating (O4Li2)(2-) dianions. Each such dianion is positioned approximately normal with respect to the other. Bonding within the breastplate structure involves a combination of mu (3)-Li. mu (4)-M, mu (3)-O, and mu (4)-O centers. Ab initio MO calculations on model systems predict that formation of the heterometallic breastplate from the exclusively mu (3)-bonded frameworks of its component homometallic structures is a favorable exothermic process. Best regarded as an inherently stable contacted triple ion sandwich comprising a dianion-tetramonocation-dianion arrangement, the breastplate motif is likely to be more widely applicable within heterometallic structural chemistry than so far recognized. This point is discussed with reference to a previously documented series of heterometallic p-block metal-based imide structures of general formula [(CyN)(8)(M4M42)-M-1], where M-1 = Sb or As and M-2 = Ag, Cu, or Na.

KW - molecular orbital methods

KW - x-rays

KW - crystal structures

KW - basis sets

KW - cage complex

KW - potassium

KW - ligands

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DO - 10.1021/ja002217z

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JO - Journal of the American Chemical Society

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JF - Journal of the American Chemical Society

SN - 0002-7863

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