Dinuclear Ru–Aqua Complexes for Selective Epoxidation Catalysis Based on Supramolecular Substrate Orientation Effects

Ru-aqua complex {[Ru^II(trpy)(H₂O)]₂(μ-pyr-dc)}⁺ is a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes. High turnover numbers (TNs), up to 17000, and turnover frequencies (TOF), up to 24120 h⁻¹ (6.7 s⁻¹), have been obtained using PhIO as oxidant. This species presents an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides. In addition, it shows different reactivity to cis and trans olefins due to a substrate orientation supramolecular effect transmitted by its ligand scaffold. This effect together with the impressive reaction rates are rationalized using electrochemical techniques and DFT calculations.