Radical anion of isolable dialkylsilylene.
By the reduction of an isolable dialkylsilylene, 2,2,5,5-[tetrakis(trimethylsilyl)]-1-silacyclopentane-1,1-diyl (1), with cesium, rubidium, potassium, sodium, and lithium 4,4'-di(tert-butyl)biphenylide in DME at low temperatures, the corresponding silylene radical anion 2 was generated as the first persistent silylene radical anion in solution and characterized by ESR spectroscopy. Radical anion 2 is rather stable at -70 degrees C in DME but decomposes rapidly at room temperature with a half-life time of ca. 20 min. The g-factor and 29Si hyperfine splitting constants (hfs's) of 2 are almost independent of the countercations, indicating that 2 exists as a free ion or a solvent-separated ion pair in a polar DME solution. A very small hfs due to the 29Si nucleus of the divalent silicon (3.0 mT) as well as a very large g-factor (2.0077) indicates that an unpaired electron is accommodated in the vacant 3ppi orbital of silylene 1.
Ishida
S
S
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578, Japan.
Iwamoto
T
T
Kira
M
M