Strathprints logo
Strathprints Home | Open Access | Browse | Search | User area | Copyright | Help | Library Home | SUPrimo

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 and Clegg, W and Drummond, A M and Liddle, S T and Mulvey, Robert (2000) A remarkable isostructural homologous series of mixed lithium-heavier alkali metal tert-butoxides [(t-BuO)(8)Li4M4] (M = Na, K, Rb or Cs). Journal of the American Chemical Society, 122 (45). pp. 11117-11124. ISSN 0002-7863

Full text not available in this repository. (Request a copy from the Strathclyde author)

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.

Item type: Article
ID code: 38326
Keywords: molecular orbital methods, x-rays, crystal structures, basis sets, cage complex, potassium, ligands, Chemistry, Biochemistry, Colloid and Surface Chemistry, Chemistry(all), Catalysis
Subjects: Science > Chemistry
Department: Faculty of Science > Pure and Applied Chemistry
Related URLs:
    Depositing user: Pure Administrator
    Date Deposited: 08 Mar 2012 14:09
    Last modified: 05 Sep 2014 15:27
    URI: http://strathprints.strath.ac.uk/id/eprint/38326

    Actions (login required)

    View Item