AbstractRhodium(III) and ruthenium(II) complexes supported by a pentadentate tetrapodal (pentaPod) phosphine ligand are synthesized through abstraction of one chloride ligand from initially obtained κ4‐pentaPod coordinated dichloro complexes [MCl2(κ4‐P2MePP2Ph)]+/0 (M=Rh(III), Ru(II)) with alkali salts of weakly coordinating anions. While for the rhodium κ5‐pentaPod complex the remaining, axial chloride ligand could not be replaced by di‐ or triatomic ligands, in case of ruthenium the complexes [Ru(CN)(κ5‐P2MePP2Ph]Al(pftb)4 (5) and [Ru(N3)(κ5‐P2MePP2Ph]Al(pftb)4 (6) could be generated through ligand exchange. By comparison of NMR parameters and employing DFT calculations, additional insights into the electronic influence of different ligands (i. e., Cl−, CN−, N3−) could be gained.