title: Dinuclear Ru-aqua complexes for selective epoxidation catalysis based on supramolecular substrate orientation effects.
abstract: 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.
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 43007 Tarragona (Spain), Departament de Química, Universitat Autònoma de Barcelona Cerdanyola del Vallès, 08193, Barcelona (Spain).
authors.forename: Carlo
authors.initials: C
authors.lastname: Di Giovanni
authors.forename: Albert
authors.initials: A
authors.lastname: Poater
authors.forename: Jordi
authors.initials: J
authors.lastname: Benet-Buchholz
authors.forename: Luigi
authors.initials: L
authors.lastname: Cavallo
authors.forename: Miquel
authors.initials: M
authors.lastname: Solà
authors.forename: Antoni
authors.initials: A
authors.lastname: Llobet
keywords: density functional calculations; electrochemistry; epoxidation; ruthenium; supramolecular redox catalysis