Reactions of [PhI(pyridine)<sub>2</sub>]<sup>2+</sup> with Model Pd and Pt II/IV Redox Couples
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Abstract
The results of the
reactions of the dicationic iodine(III) family of oxidants [PhI(pyridine)<sub>2</sub>]<sup>2+</sup> 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
