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Tetrahedranyllithium:  Synthesis, Characterization, and Reactivity

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Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan
Cite this: J. Am. Chem. Soc. 2003, 125, 42, 12684–12685
Publication Date (Web):September 26, 2003
https://doi.org/10.1021/ja030476t
Copyright © 2003 American Chemical Society
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Abstract

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The first representative of stable tetrahedranyl anion, tris(trimethylsilyl)tetrahedranyllithium (3), has been synthesized by the reaction of tetrakis(trimethylsilyl)tetrahedrane (2) with methyllithium in tetrahydrofuran. The structural characterization of the tetrahedranyllithium has been achieved by X-ray crystallography, showing that the structure of 3·(TMEDA)1.5 represents a stretched tetrahedron. The endocyclic C(Li)−C(SiMe3) bond lengths range from 1.5408(15) to 1.5441(15) Å (av 1.5425(15) Å), and are longer than the endocyclic C(SiMe3)−C(SiMe3) bond lengths, which range from 1.4961(15) to 1.5009(15) Å (av 1.4986(15) Å). Methyl- and hydrogen-substituted tetrahedranes have also been prepared by the reaction of 3 with dimethyl sulfate and cyclopentadiene, respectively.

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Experimental procedures, spectral data, tables of crystallographic data including atomic positional and thermal parameters for 3 (PDF). X-ray crystallographic file in CIF format. This material is available free of charge via the Internet at http://pubs.acs.org.

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