Cooperative activating effects of metal ion and Brønsted acid on a metal oxo species

Abstract

Metal oxo (MO) complexes are common oxidants in chemical and biological systems. The use of Lewis acids to activate metal oxo species has attracted great interest in recent years, especially after the discovery of the CaMn₄O₅ cluster in the oxygen-evolving centre of photosystem II. Strong Lewis acids such as Sc³⁺ and BF₃, as well as strong Brønsted acids such as H₂SO₄ and CF₃SO₃H, are commonly used to activate metal oxo species. In this work, we demonstrate that relatively weak Lewis acids such as Ca²⁺ and other group 2 metal ions, as well as weak Brønsted acids such as CH₃CO₂H, can readily activate the stable RuO₄⁻ complex towards the oxidation of alkanes. Notably, the use of Ca²⁺ and CH₃CO₂H together produces a remarkable cooperative effect on RuO₄⁻, resulting in a much more efficient oxidant. DFT calculations show that Ca²⁺ and CH₃CO₂H can bind to two oxo ligands to form a chelate ring. This results in substantial lowering of the barrier for hydrogen atom abstraction from cyclohexane.