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Metal Azolate/Carboxylate Frameworks as Catalysts in Oxidative and C-C Coupling Reactions

2016-06Journal article Restricted access
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dc.contributor.authorTabacaru, Aurel
dc.contributor.authorXhaferaj, Nertil
dc.contributor.authorMartins, Luisa
dc.contributor.authorAlegria, Elisabete
dc.contributor.authorChay, Rogério
dc.contributor.authorGiacobbe, Carlotta
dc.contributor.authorDomasevitch, Konstantin V.
dc.contributor.authorPombeiro, Armando
dc.contributor.authorGALLI, SIMONA
dc.contributor.authorPettinari, Claudio
dc.date.accessioned2017-07-25T09:46:39Z
dc.date.available2017-07-25T09:46:39Z
dc.date.issued2016-06
dc.description.abstractThe five metal azolate/carboxylate (MAC) compounds [Cd(dmpzc)(DMF)(H2O)] (Cd-d.mpzc), [Pd-(H(2)dmpzc)(2)Cl-2] (Pd.dmpzc), [Cu(Hdmpzc)(2)] (Cu-dmpzc), [Zn4O(dmpzc)(3)]-Solv (Zn-dmpzcS), and [Co4O(dmpz(3)]-Solv (Co-dinpzcS) were isolated by coupling 3,5-dimethy1-1H-pyrazol-4-carboxylic acid (H(2)dmpzc) to cadmium(II), palladium(II), copper(II), zinc(II), and cobalt(II) salts. While Cd-clinpzc and Pd-dmpzc had never been prepared in the past, for Cu-dmpzc, Zndmpzc"S, and Co-dmpzc"S we optimized alternative synthetic paths that, in the case of the copper(II) and cobalt(11) derivatives, are faster and grant higher yields than the previously reported ones. The crystal structure details were determined ab initio (Cd-dmpzc and Pd-dmpzc) or refined (Cu-dmpzc, Zn-dmpzc"S, and Co-dmpzc-S) by means of powder X-ray diffraction (PXRD). While Cd-dmpzc is a nonporous 3D MAC framework, Pddmpzc shows a 3D hybrid coordination/hydrogen-bonded network, in which Pd(H(2)dmpzc)(2)Cl-2 monomers are present. The thermal behavior of the five MAC compounds was investigated by coupling thermal analysis to variable-temperature PXRD. Their catalytic activity was assessed in oxidative and C C coupling reactions, with the copper(II) and cadmium(II) derivatives being the first nonporous MAC frameworks to be tested as catalysts. Cu-dmpzc is the most active catalyst in the partial oxidation of cydohexane by tert-butyl hydropermdde in acetonitrile (yields up to 12% after 9 h) and is remarkably active in the solvent-free microwave-assisted oxidation of 1-phenylethanol to acetophenone (yields up to 99% at 120 degrees C in only 0.5 h). On the other hand, activated Zn-dmpzc"S (Zn-dmpzc) is the most active catalyst in the Henry C C coupling reaction of aromatic aldehydes with nitroethane, showing appreciable diastereoselectivity toward the syn-nitroalkanol isomer (syn:anti selectivity up to 79:21).pt_PT
dc.description.versioninfo:eu-repo/semantics/publishedVersionpt_PT
dc.identifier.citationTABACARU, Aure [et al] - Metal Azolate/Carboxylate Frameworks as Catalysts in Oxidative and C-C Coupling Reactions. Inorganic Chemistry. ISSN: 0020-1669. Vol. 55, N.º12 (2016), pp. 51-57pt_PT
dc.identifier.doi10.1021/acs.inorgchem.5b02997pt_PT
dc.identifier.issn0020-1669
dc.identifier.urihttp://hdl.handle.net/10400.21/7304
dc.language.isoengpt_PT
dc.peerreviewedyespt_PT
dc.relation.publisherversionfile:///C:/Users/utilizador2/Desktop/Metal%20Azolate%20Carboxylate_MLu%C3%ADsa_.pdfpt_PT
dc.titleMetal Azolate/Carboxylate Frameworks as Catalysts in Oxidative and C-C Coupling Reactionspt_PT
dc.typejournal article
dspace.entity.typePublication
oaire.citation.endPage57pt_PT
oaire.citation.issue12pt_PT
oaire.citation.startPage51pt_PT
oaire.citation.titleINORGANIC CHEMISTRYpt_PT
oaire.citation.volume55pt_PT
person.familyNameTabacaru
person.familyNameMartins
person.familyNameAlegria
person.familyNameChay
person.familyNameGiacobbe
person.familyNamePombeiro
person.familyNameGALLI
person.familyNamePettinari
person.givenNameAurel
person.givenNameLuisa
person.givenNameElisabete
person.givenNameRogério
person.givenNameCarlotta
person.givenNameArmando
person.givenNameSIMONA
person.givenNameClaudio
person.identifier637885
person.identifier863202
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person.identifier.ciencia-id8311-38FA-CEFB
person.identifier.orcid0000-0001-7677-4473
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person.identifier.orcid0000-0003-4060-1057
person.identifier.orcid0000-0002-9213-5214
person.identifier.orcid0000-0003-2988-5992
person.identifier.orcid0000-0001-8323-888X
person.identifier.orcid0000-0003-0335-5707
person.identifier.orcid0000-0002-2547-7206
person.identifier.ridD-2069-2012
person.identifier.ridG-6210-2011
person.identifier.ridE-9945-2012
person.identifier.ridI-5945-2012
person.identifier.scopus-author-id54394264500
person.identifier.scopus-author-id8650947800
person.identifier.scopus-author-id8315848300
person.identifier.scopus-author-id7006067269
person.identifier.scopus-author-id7102963193
person.identifier.scopus-author-id7006581579
rcaap.rightsclosedAccesspt_PT
rcaap.typearticlept_PT
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