ion of chloride from (PPh3)2Pt(O,O‘-PhD-N,N‘)Ru(PPh3)2Cl2 (1) in the presence of two-electron donor ligands L results in a series of cationic Pt/Ru complexes, [(PPh3)2Pt(O,O‘-PhD-N,N‘)Ru(PPh3)2Cl(L)]PF6 (2, L = CO; 3, L = CH3CN) and [(PPh3)2Pt(O,O‘-PhD-N,N‘)Ru(PPh3)Cl(3,5-lutidine)2]PF6 (4). The redox potentials for the Ru(III/II) couples of 2 − 4 shift positive relative to that of 1 and reflect the electron demand of the ligand framework around ruthenium. The position of the Ru(III/II) wave with respect to the ligand waves is dependent on L.