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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)

Lookup NU author(s): Professor William Clegg, Dr Stephen Liddle

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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.


Publication metadata

Author(s): Armstrong DR, Clegg W, Drummond AM, Liddle ST, Mulvey RE

Publication type: Article

Publication status: Published

Journal: Journal of the American Chemical Society

Year: 2000

Volume: 122

Issue: 45

Pages: 11117-11124

ISSN (print): 0002-7863

ISSN (electronic): 1520-5126

Publisher: American Chemical Society

URL: .http:/dx.doi.org/

DOI: 10.1021/ja002217z


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