A comparative study of reactions of saccharinate (sac), thiosaccharinate (tsac) and benzisothiozolinate (bit) with trans-[PdCl 2 (H 2 NBz) 2 ] is reported. While in all cases substitution of both chlorides occurs, product types differ for the three closely related ligands. With sodium saccharinate, trans-[Pd(N-sac) 2 (H 2 NBz) 2 ] results in which the sac ligands are N-bound. A similar N-bound coordination is observed with sodium benzisothiazolinate, but a crystal structure shows that they adopt a mutual cis arrangement in cis-[Pd(N-bit) 2 (H 2 NBz) 2 ]. In contrast, with sodium thiosaccharinate it is proposed that the new ligands adopt an S-bound coordination mode in trans-[Pd(S-tsac) 2 (H 2 NBz) 2 ].