Reaction of H2SnPh2 with [Pd(dmpe)2]n (n = 1 or 2; dmpe = 1,2-bis(dimethylphosphino)ethane) in 4:1 ratio produces a tetrastannapalladacyclopentane, [Pd(SnPh2SnPh2SnPh2SnPh2)(dmpe)] (1), via dehydrogenative Sn−Sn bond formation. Heating of 1 in toluene at 70 °C cleaves the Sn−Sn bonds, which is accompanied by migration of Ph groups, to form a bis(triphenylstannyl)palladium complex, [Pd(SnPh3)2(dmpe)] (2). A similar reaction of H2SnPh2 with [Pd(PCy3)2] yields a dipalladium(I) complex with bridging diphenylstannyl ligands, [{Pd(PCy3)}2(μ-η2-HSnPh2)2] (3).