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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

© Chemistry - A European Journal, 2014, vol. 20, p. 3898-3902

Wiley-VCH Verlag

Author: Di Giovanni, Carlo
Poater Teixidor, Albert
Benet Buchholz, Jordi
Cavallo, Luigi
Solà i Puig, Miquel
Llobet Dalmases, Antoni
Date: 2014 April 1
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
ISSN: 0947-6539 (versió paper)
1521-3765 (versió electrònica)
Document access: http://hdl.handle.net/10256/10343
Language: eng
Publisher: Wiley-VCH Verlag
Collection: MICINN/PN 2012-2015/RYC-2009-05226
MICINN/PN 2012-2014/CTQ2011-23156
MINECO/PN 2011-2013/CTQ2010-21497
MINECO/PN 2011-2014/PRI-PIBIN-2011-1278
AGAUR/2009-2014/2009 SGR-637
Reproducció digital del document publicat a: http://dx.doi.org/10.1002/chem.201304699
Articles publicats (D-Q)
info:eu-repo/grantAgreement/EC/FP7/293900
Is part of: © Chemistry - A European Journal, 2014, vol. 20, p. 3898-3902
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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