Synthesis, molecular structure, and reactivity of the isolable silylenoid with a tricoordinate silicon.
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:.
Molev
Gregory
G
Department of Chemistry and the Lise Meitner Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Haifa 32000, Israel. chrbrzh@tx.technion.ac.il
Bravo-Zhivotovskii
Dmitry
D
Karni
Miriam
M
Tumanskii
Boris
B
Botoshansky
Mark
M
Apeloig
Yitzhak
Y