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

作者：Di Giovanni Carlo; Poater Albert^*; Benet Buchholz Jordi; Cavallo Luigi; Sola Miquel; Llobet Antoni

来源：Chemistry - A European Journal, 2014, 20(14): 3898-3902.

DOI：10.1002/chem.201304699

• density functional calculations
• electrochemistry
• epoxidation
• ruthenium
• supramolecular redox catalysis

Ru-aqua complex {[Ru-II(trpy)(H2O)](2)(-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 24120h(-1) (6.7s(-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.

• 出版日期2014-4-1
• 单位KAUST