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The Heavy Analogue of CpLi:  Lithium 1,2-Disila-3-germacyclopentadienide, a 6π-Electron Aromatic System

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Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan
Cite this: J. Am. Chem. Soc. 2005, 127, 38, 13142–13143
Publication Date (Web):August 31, 2005
https://doi.org/10.1021/ja054398g
Copyright © 2005 American Chemical Society
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Abstract

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Lithium 1,2-disila-3-germacyclopentadienide 2-·Li+ was synthesized by the reduction of 1,2-disila-3-germacyclopenta-2,4-diene 1 with potassium graphite followed by treatment with an excess amount of LiBr. The X-ray analysis of 2-·[Li+(THF)] revealed a delocalized aromatic cyclopentadienide-type structure with the diagnostic η5-coordination of the Li+ cation to the five-membered ring. Aromaticity of this compound was verified and confirmed by theoretical calculations. The solution behavior of the 2-·Li+ is different in nonpolar and polar solvents; in nonpolar toluene, 2-·Li+ maintained the properties of a delocalized aromatic compound with the characteristically shielded 7Li NMR resonance at −5.4 ppm, whereas in polar THF, 2-·Li+ exhibited the properties of a localized nonaromatic compound with the negative charge situated on the Ge atom.

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Experimental procedures and spectral data for compound 2-·Li+, tables of crystallographic data, including atomic positional and thermal parameters for 2-·[Li+(THF)] (PDF). This material is available free of charge via the Internet at http://pubs.acs.org.

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