Di-organotin(IV)halides R2SnCl2 (R=Me or Ph) react with bis(diphenylphosphine)methane (DPPM) and bis(diphenylphosphine)ethane (DPPE) in ethanol in aerobic conditions yielding 1:1 adducts [R2SnCl2(DPPM–O2)] and [R2SnCl2(DPPE–O2)], respectively, containing the bis(diphenylphosphine) in oxidized form. The 1:1 adduct [SnMe2Cl2(DPPM–O2)] is composed of separate molecules containing six-coordinate tin, with the ligands coordinated in the bidentate O2-fashion, whereas [SnMe2Cl2(DPPE–O2)] is polymeric, with octahedral and centrosymmetric (all trans) tin atoms. In inert atmosphere, the interaction between R2SnCl2 and DPPM or DPPE does not take place. Mono-organotin halides RSnCl3 (R=Me, Bun or Ph) react with DPPM and DPPE yielding 1:1 adducts [RSnCl3(DPPM)] (R=Me, Bun or Ph) and [RSnCl3(DPPE)] (R=Bun or Ph).