Evidence for a terminal Pt(iv)-oxo complex exhibiting diverse reactivity

Terminal oxo complexes of transition metals have critical roles in various biological and chemical processes. For example, the catalytic oxidation of organic molecules, some oxidative enzymatic transformations, and the activation of dioxygen on metal surfaces are all thought to involve oxo complexes. Moreover, they are believed to be key intermediates in the photocatalytic oxidation of water to give molecular oxygen, a topic of intensive global research aimed at artificial photosynthesis and water splitting. The terminal oxo ligand is a strong π-electron donor, so it readily forms stable complexes with high-valent early transition metals. As the d orbitals are filled up with valence electrons, the terminal oxo ligand becomes destabilized. Here we present evidence for a dⁿ (n > 5) terminal oxo complex that is not stabilized by an electron withdrawing ligand framework. This d⁶ Pt(iv) complex exhibits reactivity as an inter- and intramolecular oxygen donor and as an electrophile. In addition, it undergoes a water activation process leading to a terminal dihydroxo complex, which may be relevant to the mechanism of catalytic reactions such as water oxidation.