Dimethylphenyl-, methyldiphenyl-, and triphenyl-silyl-lithium react very rapidly with fluorene in tetrahydrofuran. The reaction can be followed at low temperature with a stop-flow technique. The thermodynamic constants of activation at –30° for this reaction with Ph3SiLi, MePh2SiLi, and Me2PhSiLi, respectively are: ΔG‡= 14·0, 13·6, 13·6 kcal. mole–1; ΔH‡= 6·1, 6·6, 6·2 kcal. mole–1; ΔS‡=–32·5, –28·8, –30·3 cal. mole–1 deg.–1. Addition of LiBPh4 to these systems has negligible effect on the rate constants.The fact that the replacement of phenyl by methyl produces so small a change has been discussed in relation to the constancy of λmax. for R3SiLi as phenyl is replaced by methyl.For the reaction of MePh2SiLi with fluorene at –30° in dimethoxyethane the thermodynamic constants of activation are: ΔG‡= 11·7 kcal. mole–1; ΔH‡= 3·5 kcal. mole–1; ΔS‡=–33·7 cal. mole–1 deg–1.Hexamethyldisilane has been cleaved by lithium in tetrahydrofuran solution to give trimethyl-silyl-lithium, and the reaction of this with fluorene has been studied qualitatively.