Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 7, Pages 1786-+Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201711426
Keywords
agostic interactions; lithium; organometallic chemistry; solid-state structures; structure elucidation
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- MENESR
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Understanding and controlling the aggregation state is germane to alkyllithium chemistry. Lewis base-free alkyllithium compounds normally form tetrahedral tetramers or octahedral hexamers in the solid state with the lithium cations being three-coordinate. We report that the unsupported cyclopropyl derivative 1-(trimethylsilyl) cyclopropyllithium [{mu-c-C(SiMe3)C2H4}Li](4) (1), synthesized by the reduction of 1(-phenylthio)-1-(trimethylsilyl) cyclopropane, crystallizes as a tetramer in the space group I-4 with the two-coordinate lithium atoms forming a square. CC agostic interactions complete the coordination sphere around each lithium. The aggregate is preserved in hydrocarbon solution. Furthermore, CC agostic interactions compete intra- and intermolecularly with Lewis base donation as in the unsaturated dimer of 1-(phenylthio) cyclopropyllithium [Li(thf)(2){mu-c-C(SPh)C2H4}(2)Li (thf)] (3) which is also fully characterized.
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