Molev Gregory, Bravo-Zhivotovskii Dmitry, Karni Miriam, Tumanskii Boris, Botoshansky Mark, Apeloig Yitzhak
Department of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel.
J Am Chem Soc. 2006 Mar 8;128(9):2784-5. doi: 10.1021/ja0575880.
The first tricoordinate fluorosilylenoid, (t-Bu2MeSi)2SiFLi.3THF (1), was synthesized, and its X-ray molecular structure was determined. 1 was synthesized in 40% yield by a bromine-lithium exchange reaction in THF of the corresponding fluorobromosilane with t-Bu2MeSiLi. 1 is best described as an R2SiF- anion attracted to a (Li.3THF)+ cation with a small contribution of resonance structure that consists of a silylene fragment and FLi.3THF. 1 reacts as a nucleophile with MeCl, PhH2SiCl, H2O, and MeOH, as an electrophile with MeLi, and as a silylene with Li (or t-BuLi) and Na, yielding alpha-lithium and alpha-sodium silyl radicals, respectively. Either photolysis or thermolysis of 1 yields the corresponding disilene R2Si=SiR2 (R = t-Bu2MeSi), probably via dimerization of R2Si:.
