Fine-Tuning the Basicity of Metal Complexes: Reversible Oxidative Addition of Se−Se Bonds to Platinum(II) Precursors

The oxidative addition of diselenides to novel platinum(II) precursors affording octahedral platinum-(IV) products was investigated. The properties of the substituents on Pt were finely tailored in order to prompt easy reversibility of the reaction. This allowed the achievement of the first example of equilibrium of oxidative addition of an E-E bond (E - chalcogen) to a Pt(II) precursor. The equilibrium constants could be evaluated by NMR spectroscopy, and the results were preliminarily rationalized in terms of steric and electronic factors.