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Dinuclear ru-aqua complexes for selective epoxidation catalysis based on supramolecular substrate orientation effects

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 for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides

This research was supported financially by MINECO (CTQ2011-23156/BQU, CTQ2010-21497 and PRI-PIBIN-2011-1278), ICIQ, FEDER fund (UNGI08-4E-003), ICREA Academia, Generalitat de Catalunya (2009SGR637); Ramon y Cajal contract (RYC-2009-05226) of MINECO, and Career Integration Grant (CIG09-GA-2011-293900) of the European Commission. COST Actions CM1205 and CM1202 are also gratefully acknowledged

Wiley-VCH Verlag

Manager: Ministerio de Economía y Competitividad (Espanya)
Generalitat de Catalunya. Agència de Gestió d’Ajuts Universitaris i de Recerca
Author: Di Giovanni, Carlo
Poater Teixidor, Albert
Benet Buchholz, Jordi
Cavallo, Luigi
Solà i Puig, Miquel
Llobet Dalmases, Antoni
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 for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides
This research was supported financially by MINECO (CTQ2011-23156/BQU, CTQ2010-21497 and PRI-PIBIN-2011-1278), ICIQ, FEDER fund (UNGI08-4E-003), ICREA Academia, Generalitat de Catalunya (2009SGR637); Ramon y Cajal contract (RYC-2009-05226) of MINECO, and Career Integration Grant (CIG09-GA-2011-293900) of the European Commission. COST Actions CM1205 and CM1202 are also gratefully acknowledged
Format: application/pdf
Document access: http://hdl.handle.net/10256/10343
Language: eng
Publisher: Wiley-VCH Verlag
Collection: info:eu-repo/semantics/altIdentifier/doi/10.1002/chem.201304699
info:eu-repo/semantics/altIdentifier/issn/0947-6539
info:eu-repo/semantics/altIdentifier/eissn/1521-3765
info:eu-repo/grantAgreement/MICINN//RYC-2009-05226/ES/RYC-2009-05226/
info:eu-repo/grantAgreement/MICINN//CTQ2011-23156/ES/AVANCES EN CATALISIS Y AROMATICIDAD/
info:eu-repo/grantAgreement/MICINN//CTQ2010-21497/ES/CATALIZADORES PARA LA FOTOSINTESIS ARTIFICIAL/
info:eu-repo/grantAgreement/MICINN//PRI-PIBIN-2011-1278/ES/Catalizadores de oxidacion de agua cotentiendo ligandos redox no-inocentes: hacia los combustibles s/
AGAUR/2009-2014/2009 SGR-637
info:eu-repo/grantAgreement/EC/FP7/293900/EU/Ab initio Statics and Molecular Dynamics Simulation of Olefin Metathesis Catalysts for pharmacological purposes/COMPUTEDRUG
Rights: Tots els drets reservats
Subject: Funcional de densitat, Teoria del
Density functionals
Electroquímica
Electrochemistry
Ruteni
Ruthenium
Catalitzadors
Catalysts
Epòxids
Epoxy compounds
Title: Dinuclear ru-aqua complexes for selective epoxidation catalysis based on supramolecular substrate orientation effects
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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