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

by C. Di Giovanni, A. Poater, J. Benet-Buchholz, L. Cavallo, M. Sola, A. Llobet
Year: 2014 ISSN: 09476539 DOI: DOI: 10.1002/chem.201304699

Bibliography

Dinuclear Ru-Aqua Complexes for Selective Epoxidation Catalysis Based on Supramolecular Substrate Orientation Effects
C. Di Giovanni, A. Poater, J. Benet-Buchholz, L. Cavallo, M. Sola, A. Llobet
Chem. Eur. J. 20, 3898, (2014)

Extra Information

Chemistry A European Journal.

Abstract

Ru-aqua complex {[RuII(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. A new Ru-aqua complex that behaves as a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes is reported. High turnover numbers and frequencies are obtained by using PhIO as oxidant. The complex shows an outstanding stereospecificity forboth cis and trans olefins towards the formation of their corresponding cis and trans epoxides (see figure).

 

 10.1002/chem.201304699

Keywords

Density functional calculations Electrochemistry Epoxidation Ruthenium Supramolecular redox catalysis