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Powerful Bis-facially Pyrazolate-Bridged Dinuclear Ruthenium Epoxidation Catalyst

A new bis-facial dinuclear ruthenium complex, {[RuII(bpy)]2(μ-bimp)(μ-Cl)}2+, 22+, containing a hexadentate pyrazolate- bridging ligand (Hbimp) and bpy as auxiliary ligands has been synthesized and fully characterized in solution by spectrometric, spectroscopic, and electrochemical techniques. The new compound has been tested with regard to its capacity to oxidize water and alkenes. The in situ generated bis-aqua complex, {[RuII(bpy)(H2O)]2(μ-bimp)}3+, 33+, is an excellent catalyst for the epoxidation of a wide range of alkenes. High turnover numbers (TN), up to 1900, and turnover frequencies (TOF), up to 73 min−1, are achieved using PhIO as oxidant. Moreover, 33+ presents an outstanding stereospecificity for both cis and trans olefins toward the formation of their corresponding epoxides due to specific interactions transmitted by its ligand scaffold. A mechanistic analysis of the epoxidation process has been performed based on density functional theory (DFT) calculations in order to better understand the putative cooperative effects within this dinuclear catalyst

Support form MINECO (Grants CTQ2011-26440, CTQ-2013-49075-R and CTQ2010-21532-C02-02) and the DFG (Grant Me1313/9-1) is gratefully acknowledged. J.A. is grateful for the award of a PIF doctoral grant from UAB. A.P. thanks the Spanish MINECO for the project CTQ2014-59832-JIN and the European Commission for a Career Integration Grant (No.CIG09-GA-2011-293900)

American Chemical Society (ACS)

Manager: Ministerio de Economía y Competitividad (Espanya)
Author: Aguiló, Joan
Francàs, Laia
Bofill, Roger
Gil-Sepulcre, Marcos
García-Antón, Jordi
Poater Teixidor, Albert
Llobet Dalmases, Antoni
Escriche, Lluís
Meyer, Franc
Sala Román, Xavier
Date: 2015
Abstract: A new bis-facial dinuclear ruthenium complex, {[RuII(bpy)]2(μ-bimp)(μ-Cl)}2+, 22+, containing a hexadentate pyrazolate- bridging ligand (Hbimp) and bpy as auxiliary ligands has been synthesized and fully characterized in solution by spectrometric, spectroscopic, and electrochemical techniques. The new compound has been tested with regard to its capacity to oxidize water and alkenes. The in situ generated bis-aqua complex, {[RuII(bpy)(H2O)]2(μ-bimp)}3+, 33+, is an excellent catalyst for the epoxidation of a wide range of alkenes. High turnover numbers (TN), up to 1900, and turnover frequencies (TOF), up to 73 min−1, are achieved using PhIO as oxidant. Moreover, 33+ presents an outstanding stereospecificity for both cis and trans olefins toward the formation of their corresponding epoxides due to specific interactions transmitted by its ligand scaffold. A mechanistic analysis of the epoxidation process has been performed based on density functional theory (DFT) calculations in order to better understand the putative cooperative effects within this dinuclear catalyst
Support form MINECO (Grants CTQ2011-26440, CTQ-2013-49075-R and CTQ2010-21532-C02-02) and the DFG (Grant Me1313/9-1) is gratefully acknowledged. J.A. is grateful for the award of a PIF doctoral grant from UAB. A.P. thanks the Spanish MINECO for the project CTQ2014-59832-JIN and the European Commission for a Career Integration Grant (No.CIG09-GA-2011-293900)
Format: application/pdf
Document access: http://hdl.handle.net/10256/12375
Language: eng
Publisher: American Chemical Society (ACS)
Collection: info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.inorgchem.5b00641
info:eu-repo/semantics/altIdentifier/issn/0020-1669
info:eu-repo/semantics/altIdentifier/eissn/1520-510X
MINECO/PE 2015-2018/CTQ2014-59832-JIN 
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: Catalitzadors
Catalysts
Epòxids
Epoxy compounds
Funcional de densitat, Teoria del
Density functionals
Electroquímica
Electrochemistry
Ruteni
Ruthenium
Title: Powerful Bis-facially Pyrazolate-Bridged Dinuclear Ruthenium Epoxidation Catalyst
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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