Lithium-tris(trimethylsilyl)methane (TsiLi) reacts with fluorosilanes via LiF elimination to yield compounds of the type TsiSiFR,R′ (R, R′ = alkyl, aryl). The hydrolyzability and the products of hydrolysis of the fluorosilyl-substituted tris(silyl)methanes vary considerably. TsiSiFR 2 compounds are resistant to hydrolysis. The compounds TsiSiF 3 (I) and TsiSiF 2Me (II) condense when hydrolyzed. The initial fluorosilanol, TsiSiF(OH)Me, can be isolated. The compounds TsiSiF 2R (R = CHMe 2 (III), C 6H 5 (IV), CMe 3(V)) hydrolyze via 1,3-migration of a silyl group to give the corresponding 1,3-disiloxanes (Me 3Si) 2CHSi(F)ROSiMe 3 (R = CHMe 2 (XII), C 6H 5 (XIII), CMe 3 (XIV)). By metallation and reaction with Me 3SiCl XIII can be converted into the tris(silyl)methyl compound TsiSi(F)C 6H 5OSiMe 3 (XV). XV can also be obtained from IV and LiOSiMe 3. The product of the second hydrolysis of IV is 1-hydroxy-1,3-disiloxane (Me 3Si) 2CHSi(OH)C 6H 5OSiMe 3 (XVI) that of V is a 1,3,5-trisiloxane Me 3SiCH 2SiCMe 3 (OSiMe 3) 2 (XVII). The 1,3,5-trisiloxane (Me 3Si) 2CHSiC 6H 5(OSiMe 3) 2 (XIX) is formed from lithiated XVI and Me 3SiCl. The structural isomers XVIII (TsiSi(OH)C 6H 5OSiMe 3) and XIX are the hydrolysis products of XV. XVII reacts with MeLi and SiF 4 via elimination of ME 4Si to yield the 1,3,5,7,9-pentasiloxane [(Me 3SiCH 2)CMe 3Si(OSiMe 3)O] 2SiF 2 (XX). Br 2 brominates the phenyl ring of the fluoro-containing compounds IV and XIII, giving (Me 3Si) 3CSiF(R)C 6H 5Br (R = F (XXI), OSiMe 3 (XXII)). C 6H 5Br elimination during the formation of (Me 3Si) 2CHSiBr (OSiMe 3) 2 (XXIII) occurs in the reaction with XIX. The products of the reaction of XXIII with Me 3SiCl, after lithiation, are the tris(silyl) compound TsiSiBr(OSiMe 3) 2 (XXIV) and the disilane [TsiSi(OSiMe 3) 2] 2 (XXV).