A series of diphosphine ligands (Pr2P)-Pr-i-C6H4-X-C6H4-(PPr2)-Pr-i (for ligand L-1, X = CH2; for ligand L-2, X = CH2CH2) was investigated to determine the preference for cis/trans coordination to palladium(0), palladium(11), and rhodium(I). Increasing the length of the bridging alkyl backbone from one to two carbons changes the geometry of the resulting palladium(II) complexes, with L-1 coordinating preferentially cis, while L-2 coordinates in a trans fashion. Coordination to Pd(0) leads to (LPd)-Pd-1(dba) and (LPd)-Pd-2(dba), in which both ligands accommodate a P-M-P angle close to 120 degrees. L-2 was found to coordinate cis in a rhodium(I) complex ([(LRh)-Rh-2(nbd)][BF4], where nbd = norbornadiene).