Oxidative reactions are reported to alkyl or phenyl halides, the chloromethanes CH 4− n Cl nn ( n = 2, 3, or 4), or N-bromohexamethyldisilazane with (i) some bulky germanium(II), tin(II), or lead(II) amides, or (ii) bis[bis(trimethylsilyl)methyl]tin(II). Similar reactions with pivaloyl or benzoyl chloride, or trifluoroacetic anhydride, produced stable, yellow α-keto-germanes and -stannanes. The following new compounds have been isolated and characterised: Sn(NR) 2) 2(R′)X, (R = SiMe 3; R′X = Bu nCl, MeBr, EtBr, Pr nBr, Bu tBr, PhBr, MeI, EtI, Pr iI, Bu nI, PhI, CCl 4, CHCl 3, or CH 2Cl 2, MBr(NR 2) 3 (M = Ge, Sn, or Pb; R = SiMe 3), SnBr(NR 2)(TMPPD) 2 [TMPPD = NCMe 2(CH) 2) 3C Me 2]. SnIMe(TMPPD) 2, Sn(CHR 2) 3I, M′(COR″)-Cl(TMPPD) 2 (M′ = Ge OR Sn, R″ = Ph OR Bu t), Sn(CHR 2) 2(COR″)Cl, M′(COCF 3)(NR 2) 2(OCOCF 3), M′(COCF 3)(OCOCF 3)(TMPPD) 2, and M′(COCF 3)(NBu t 2) 2(OCOCF 3). The α-keto-germanes and -stannanes are particularly noteworthy. The acyl chloride 1 1 adducts (which are sparingly soluble in hydrocarbons) show two carbonyl stretching modes in the region 1635–1690 cm −1 which is attributed to the presence of two isomers as a consequence of restricted rotation about the ▪ bond. This effect is not observed in the bis(amido)metal 1 1 adducts with (CF 3CO) 2O probably because the −OC(O)CF 3 ligand, being sterically much more demanding than Cl −, directs the formation of a single rotamer. The mass spectral fragmentation pattern of GeBr[N(SiMe 3) 2] 3 is reported. The halogenohydrocarbon addition reactions to the amides M′(NR 2) 2 (R = SiMe 3) are believed to involve a free radical pathway, with M′(NR 2) 2X as an intermediate. The reaction of Sn(NR 2) 2 with excess of PhBr is pseudo first-order, and is catalysed by a trace of EtBr. The uncatalysed reaction yields exclusively SnBr(NR 2) 2Ph in C 6H 6, whereas in THF SnBr 2(NR 2) 2 is a significant by-product. Crystalline SnBr[N(SiMe 3) 2] 3 is a monomer, with SnBr 2.579(2) Å, SnN 2.056(7) Å, BrSnN 102.4(2)°, and NSnN′ 115.5(1)°; the nitrogen environment is trigonal planar.