The dinuclear anionic complexes [NBu₄][(R_F)₂M^II(μ-PPh₂)₂M'^II(N^O)] (R_F = C₆F₅. N^O = 8-hydroxyquinolinate, hq; M = M' = Pt 1; Pd 2; M = Pt, M' = Pd, 3. N^O = o-picolinate, pic; M = Pt, M' = Pt, 4; Pd, 5) are synthesized from the tetranuclear [NBu₄]₂[{(R_F)₂Pt(μ-PPh₂)₂M(μ-Cl)}₂] by the elimination of the bridging Cl as AgCl in acetone, and coordination of the corresponding N,O-donor ligand (1, 4, and 5) or connecting the fragments "cis-[(R_F)₂M(μ-PPh₂)₂]^2-" and "M'(N^O)" (2 and 3). The electrochemical oxidation of the anionic complexes 1-5 occurring under HRMS(+) conditions gave the cations [(R_F)₂M(μ-PPh₂)₂M'(N^O)]⁺, presumably endowed with a M(III),M'(III) core. The oxidative addition of I₂ to the 8-hydroxyquinolinate complexes 1-3 triggers a reductive coupling between a PPh₂ bridging ligand and the N,O-donor chelate ligand with formation of a P-O bond and ends up in complexes of platinum(II) or palladium(II) of formula [(R_F)₂M^II(μ-I)(μ-PPh₂)M'^II(P,N-PPh₂hq)], M = M' = Pt 7, Pd 8; M = Pt, M' = Pd, 9. Complexes 7-9 show a new Ph₂P-OC₉H₆N (Ph₂P-hq) ligand bonded to the metal center in a P,N-chelate mode. Analogously, the addition of I₂ to solutions of the o-picolinate complexes 4 and 5 causes the reductive coupling between a PPh₂ bridging ligand and the starting N,O-donor chelate ligand with formation of a P-O bond, forming Ph₂P-OC₆H₄NO (Ph₂P-pic). In these cases, the isolated derivatives [NBu₄][(Ph₂P-pic)(R_F)Pt^II(μ-I)(μ-PPh₂)M^II(R_F)I] (M = Pt 10, Pd 11) are anionic, as a consequence of the coordination of the resulting new phosphane ligand (Ph₂P-pic) as monodentate P-donor, and a terminal iodo group to the M atom. The oxidative addition of I₂ to [NBu₄][(R_F)₂Pt^II(μ-PPh₂)₂Pt^II(acac)] (6) (acac = acetylacetonate) also results in a reductive coupling between the diphenylphosphanido and the acetylacetonate ligand with formation of a P-O bond and synthesis of the complex [NBu₄][(R_F)₂Pt^II(μ-I)(μ-PPh₂)Pt^II(Ph₂P-acac)I] (12). The transformations of the starting complexes into the products containing the P-O ligands passes through mixed valence M(II),M'(IV) intermediates which were detected, for M = M' = Pt, by spectroscopic and spectrometric measurements.