Toggle Main Menu Toggle Search

Open Access padlockePrints

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): Emeritus Professor Bill Clegg, Dr Stephen Liddle

Downloads

Full text for this publication is not currently held within this repository. Alternative links are provided below where available.


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


Altmetrics

Altmetrics provided by Altmetric


Actions

Find at Newcastle University icon    Link to this publication


Share