Trichlorostannyl complexes [M(SnCl3)(bpy)2P]BPh4 [M = Ru, P = P(OEt)31a, PPh(OEt)21b; M = Os, P = P(OEt)32; bpy = 2,2′-bipyridine] were prepared by allowing chloro complexes [MCl(bpy)2P]BPh4 to react with SnCl2 in 1,2-dichloroethane. Bis(trichlorostannyl) compounds Ru(SnCl3)2(N–N)P2 [N–N = bpy, P = P(OEt)33a, PPh(OEt)23b; N–N = 1,10-phenanthroline (phen), P = P(OEt)34] were also prepared by reacting [RuCl(N–N)P3]BPh4 precursors with SnCl2·2H2O in ethanol. Treatment of both mono- 1a, 2 and bis 3a trichlorostannyl complexes with NaBH4 afforded mono- and bis(trihydridestannyl) derivatives [M(SnH3)(bpy)2P]BPh45, 6 and Ru(SnH3)2(bpy)P27 [P = P(OEt)3], respectively. Treatment of 1a, 2 with MgBrMe gave the trimethylstannyl complexes [M(SnMe3)(bpy)2P]BPh48, 9, and treatment of 3a afforded the bis(stannyl) Ru(SnClMe2)2(bpy)P210 derivative. Alkynylstannyl complexes [M{Sn(C
CR)3}(bpy)2P]BPh411–13 and Ru[Sn(C
CR)3]2(N–N)P214–17 (R = p-tolyl, But; N–N = bpy, phen) were also prepared by allowing trichlorostannyl compounds 1–4 to react with Li+[RC
C]− in thf. The complexes were characterised spectroscopically and by the X-ray crystal structure determination of [Ru(SnMe3)(bpy)2{P(OEt)3}]BPh48 derivative.