Reusable manganese compounds containing pyrazole-based ligands for olefin epoxidation reactions
dc.contributor.author
dc.date.accessioned
2015-12-01T11:43:03Z
dc.date.available
2016-09-22T03:00:05Z
dc.date.issued
2015-09-21
dc.identifier.issn
1477-9226
dc.identifier.uri
dc.description.abstract
We describe the synthesis of new manganese(II) and manganese(III) complexes containing the bidentate ligands 2-(3-pyrazolyl)pyridine, pypz-H, and 3(5)-(2-hydroxyphenyl)pyrazole, HOphpz-H, with formula [MnX2(pypz-H)2] (X = Cl−, 1, CF3SO3−, 2, OAc−, 3 or NO3− (4)), [MnCl2(pypz-H)(H2O)2], 5, or [MnCl- (Ophpz-H)2], 6. All the complexes have been characterized through analytical, spectroscopic and electrochemical techniques. Single X-ray structure analysis revealed a six-coordinated Mn(II) ion in complexes 1<br>5, and a five-coordinated Mn(III) ion in complex 6. Compound 5 is the first co-crystal of Mn(II) containing Cl and H2O ligands together with bidentate nitrogen ligands. The catalytic activity of complexes 1<br>6 has been tested with regard to the epoxidation of styrene and, in the case of 1, 5 and 6, other alkenes have been epoxidized using peracetic acid as oxidant in different media, among which glycerol, a green solvent never used in epoxidation reactions using peracetic acid as oxidant. The catalysts show moderate to high conversions and selectivities towards the corresponding epoxides. For complexes 1, 5 and 6, a certain degree of cis → trans isomerization is observed in the case of cis-β-methylstyrene. These observations have been explained through computational calculations. The reutilization of catalysts 1 and 6 for the epoxidation of alkenes has been evaluated in [bmim] : acetonitrile mixture (bmim = 1-butyl- 3-methylimidazolium), allowing the effective recyclability of the catalytic system and keeping high conversion and selectivity values up to 12 successive runs, in all cases
dc.description.sponsorship
This research has been financed by MINECO of Spain through projects, CTQ2010-21532-C02-01 and CTQ2014-54306-P. EM thanks UdG for a predoctoral grant. Serveis Tècnics de Recerca (STR) from UdG are also acknowledged for technical support. AP thanks the Spanish MINECO for project CTQ2014-59832- JIN and European Commission for a Career Integration Grant (CIG09-GA-2011-293900). MS thanks EU for a FEDER fund (UNGI10-4E-801) and the Generalitat de Catalunya for project 2014SGR931 and ICREA Academia 2009 prize
dc.format.extent
15 p.
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Royal Society of Chemistry (RSC)
dc.relation
info:eu-repo/grantAgreement/MICINN//CTQ2010-21532-C02-01/ES/MIMETIZACION DE PROCESOS BIOINORGANICOS Y APLICACIONES CATALITICAS CON COMPUESTOS DE METALES DE TRANSICION./
info:eu-repo/grantAgreement/MINECO//CTQ2014-54306-P/ES/ESTUDIOS TEORICO-EXPERIMENTALES DE CICLACIONES CATALIZADAS POR METALES DE TRANSICION. NUEVOS DESARROLLOS EN AROMATICIDAD, FUNCIONALES DE LA DENSIDAD Y QUIMICA SUPRAMOLECULAR/
info:eu-repo/grantAgreement/MINECO//CTQ2014-59832-JIN/ES/ESCANEO COMPUTACIONAL DE RELACIONES ESTRUCTURA%2FACTIVIDAD DE CATALIZADORES DE OXIDACION DEL AGUA PARA LA GENERACION DE H2/
AGAUR/2014-2016/2014 SGR-931
dc.relation.isformatof
Versió postprint del document publicat a: http://dx.doi.org/10.1039/c5dt02787j
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© Dalton Transactions, 2015, vol. 44, p. 17529-17543
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Articles publicats (D-Q)
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dc.rights
Tots els drets reservats
dc.source
Manrique Salas, Ester Poater Teixidor, Albert Fontrodona, Xavier Solà i Puig, Miquel Rodríguez Pizarro, Montserrat Romero García, Isabel 2015 Reusable manganese compounds containing pyrazole-based ligands for olefin epoxidation reactions Dalton Transactions 44 17529 17543
dc.title
Reusable manganese compounds containing pyrazole-based ligands for olefin epoxidation reactions
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.relation.projectID
info:eu-repo/grantAgreement/EC/FP7/293900/EU/Ab initio Statics and Molecular Dynamics Simulation of Olefin Metathesis Catalysts for pharmacological purposes/COMPUTEDRUG
dc.type.version
info:eu-repo/semantics/acceptedVersion
dc.identifier.doi
dc.identifier.idgrec
023625
dc.contributor.funder
dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
1477-9234