title: Synthesis of silenyllithiums Li(R'3Si)Si═C(SiR3)(1-Ad) via transient silyne-silylidene intermediates.
abstract: The first two lithium silenides, Li(tBu(2)MeSi)Si═C(SiMetBu(2))(1-Ad) (1) and Li(tBuMe(2)Si)Si═C(SiMetBu(2))(1-Ad) (2) were prepared by THF addition to the corresponding lithium-silenolates, [(tBu(2)MeSi)(2)Si═C(OLi)(1-Ad)]·(R(3)SiLi) (3a: R(3)Si═tBu(2)MeSi, 3b: R(3)Si═tBuMe(2)Si). 1 and 2 were crystallized, and their structures were determined by X-ray crystallography. This process requires the presence of both coaggregated silyllithium (R(3)SiLi) (3a and 3b) and THF. Based on reaction products and DFT calculations, it is suggested that elimination of tBu(2)MeSiOLi from 3a (or 3b) produces first the corresponding silyne intermediate which rearranges to the corresponding silylidene, which is then trapped by R(3)SiLi giving 1 (or 2).
authors.affiliation: Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel.
authors.forename: Lieby
authors.initials: L
authors.lastname: Zborovsky
authors.forename: Roman
authors.initials: R
authors.lastname: Dobrovetsky
authors.forename: Mark
authors.initials: M
authors.lastname: Botoshansky
authors.forename: Dmitry
authors.initials: D
authors.lastname: Bravo-Zhivotovskii
authors.forename: Yitzhak
authors.initials: Y
authors.lastname: Apeloig