The reactions between SnCl4 and (SiH3)nX have been investigated [n= 1, X = H, F, Cl, Br, SiH3, Mn(CO)5, or Co(CO)4; n= 2, X = 0 or S; n= 3, X = N or P]; the reaction with (Me2SiH)2O was also investigated. With SiH4, Si2H6, SiH3F, SiH3Cl, [SiH3Mn(CO)5], and (SiH3)3N, reaction led to monochlorination at silicon, and spectroscopic parameters for the compounds SiH2FCl, [SiH2ClMn(CO)5], ClSiH2N(SiH3)2, (ClSiH2)2NSiH3, and (ClSiH2)3N, all prepared by this route, are reported. For the amines, 29Si and 15N chemical shifts were measured by heteronuclear double resonance. Reactions with other silyl compounds led to the formation of SiH3Cl, although some evidence was obtained for the formation of intermediate trichlorostannyl species.