Reactions of [PhI(pyridine)₂]²⁺ with Model Pd and Pt II/IV Redox Couples

The results of the reactions of the dicationic iodine­(III) family of oxidants [PhI­(pyridine)₂]²⁺ with model Pd­(II) and Pt­(II) complexes are described. Depending on the specific reaction pairs, a variety of outcomes are observed. For palladium, Pd­(IV) complexes cannot be observed but are implicated in C–C and C–N bond formation for Pd­(II) starting materials based on phenylpyridine and 2,2-bipyridine, respectively. Theoretical comparisons with similar processes for −Cl and −OAc rather than pyridine indicate that these provide greater thermodynamic stability, and our results here show that they also give greater kinetic stability (the failure of MP2 methods for these systems is quite dramatic). In contrast, oxidation and delivery of the pyridine ligands gives dicationic Pt­(IV) complexes that may be isolated and structurally characterized