Repository logo
 
Publication

Hexanuclear and undecanuclear iron(III) carboxylates as catalyst precursors for cyclohexane oxidation

2013Journal article Open access
Simple item page
dc.contributor.authorMilunovic, Miljan N. M.
dc.contributor.authorMartins, Luisa
dc.contributor.authorAlegria, Elisabete
dc.contributor.authorPombeiro, Armando
dc.contributor.authorKrachler, Regina
dc.contributor.authorTrettenhahn, Guenter
dc.contributor.authorTurta, Constantin
dc.contributor.authorShova, Sergiu
dc.contributor.authorArion, Vladimir B.
dc.date.accessioned2013-11-08T11:22:19Z
dc.date.available2013-11-08T11:22:19Z
dc.date.issued2013
dc.description.abstractTwo multinuclear complexes [Fe-6(mu(3)-O)(2)(mu(4)-O-2)L-10(OAc)(2)(H2O)(2)]center dot 2.625Et(2)O center dot 2.375H(2)O (1) and [(Fe11Cl)-Cl-III-(mu(4)-O)(3)(mu(3)-O)(5)L-16(dmf)(2.5)(H2O)(0.5)]center dot Et2O center dot 1.25dmf center dot 3.8H(2)O (2), where HL = 3,4,5-trimethoxybenzoic acid and dmf = dimethylformamide, have been prepared from trinuclear iron(III) carboxylates via their structural rearrangement in dimethylformamide or diethyl ether-dimethylformamide 9:1, respectively, and slow vapor diffusion of diethyl ether into the reaction mixture. Both compounds have been characterized by X-ray diffraction, optical, Mossbauer spectroscopy, and magnetic measurements. Complex 1 possesses a hexanuclear ferric peroxido-dioxido {Fe-6(O-2)(O)(2)}(12+) core unit, which adopts a recliner conformation, while complex 2 contains an unprecedented {Fe11O8Cl}(16+) core, in which 9 ferric ions are six-coordinate and the remaining two are five-coordinate. Another structural feature of note of the undecanuclear core is the presence of a deformed cubane entity {Fe-4(mu(3)-O)(mu(4)-O)(3)}(4+). Both complexes act as catalyst precursors for the oxidation of cyclohexane to cyclohexanol and cyclohexanone with aqueous H2O2, in the presence of pyrazinecarboxylic acid. Remarkable TONs and TOFs (the latter mainly for 1) with concomitant quite good yields have been achieved under mild conditions. Moreover, 1 exhibits remarkably high activity in an exceptionally short reaction time (45 min), being unprecedented for any metal catalyzed alkane oxidation by H2O2. The catalytic reactions proceed via Fenton type chemistry.por
dc.identifier.citationMILUNOVIC, Miljan N. M.; MARTINS, Luisa M. D. R. S.; ALEGRIA, Elisabete C. B. A. ; POMBEIRO, Armando J. L.; KRACHLER, Regina; TRETTENHAHN, Guenter; TURTA, Constantin; SHOVA, Sergiu; ARION, Vladimir B. - Hexanuclear and undecanuclear iron(III) carboxylates as catalyst precursors for cyclohexane oxidation. Dalton Transactions. ISSN 1477-9226. Vol. 42, nr. 40 (2013), p. 14388-14401.por
dc.identifier.issn1477-9226
dc.identifier.other10.1039/c3dt50966d
dc.identifier.urihttp://hdl.handle.net/10400.21/2887
dc.language.isoengpor
dc.peerreviewedyespor
dc.publisherRoyal Soc Chemistrypor
dc.subjectSingle-pot hydrocarboxylationpor
dc.subjectMild peroxidative oxidationpor
dc.subjectNonheme iron catalystspor
dc.subjectCopper triethnolamine complexespor
dc.subjectHydrogen-peroxidepor
dc.subjectC-Hpor
dc.subjectAlkane hydroxylationpor
dc.subjectHighly efficientpor
dc.subjectMetal-freepor
dc.titleHexanuclear and undecanuclear iron(III) carboxylates as catalyst precursors for cyclohexane oxidationpor
dc.typejournal article
dspace.entity.typePublication
oaire.citation.conferencePlaceCambspor
oaire.citation.endPage14401por
oaire.citation.issue40por
oaire.citation.startPage14388por
oaire.citation.titleDalton Transactionspor
oaire.citation.volume42por
person.familyNameMartins
person.familyNameAlegria
person.familyNamePombeiro
person.familyNameKrachler
person.familyNameTurta
person.familyNameShova
person.givenNameLuisa
person.givenNameElisabete
person.givenNameArmando
person.givenNameRegina
person.givenNameConstantin
person.givenNameSergiu
person.identifier637885
person.identifier863202
person.identifier.ciencia-idE218-E297-A4EA
person.identifier.ciencia-id8C1F-851A-9F1C
person.identifier.ciencia-id8311-38FA-CEFB
person.identifier.orcid0000-0002-5403-9352
person.identifier.orcid0000-0003-4060-1057
person.identifier.orcid0000-0001-8323-888X
person.identifier.orcid0000-0003-3435-9575
person.identifier.orcid0000-0003-2170-9003
person.identifier.orcid0000-0002-1222-4373
person.identifier.ridG-6210-2011
person.identifier.ridE-9945-2012
person.identifier.ridI-5945-2012
person.identifier.scopus-author-id8650947800
person.identifier.scopus-author-id8315848300
person.identifier.scopus-author-id7006067269
person.identifier.scopus-author-id6604057833
person.identifier.scopus-author-id6701404110
rcaap.rightsrestrictedAccesspor
rcaap.typearticlepor
relation.isAuthorOfPublication8ed70b09-b4d3-4a5d-9f75-12b13a332204
relation.isAuthorOfPublication6d781c38-c45e-4159-b795-8c8675606160
relation.isAuthorOfPublication6d18ff2e-5c33-4010-b1e7-964c72349813
relation.isAuthorOfPublication6e608db8-1333-4b53-b5fd-95adc7fc44cd
relation.isAuthorOfPublication6e16cf9d-a970-4361-9bbc-a14caebb38cc
relation.isAuthorOfPublicationbb7f1c81-0dad-4583-9d7a-b6d705e4bc64
relation.isAuthorOfPublication.latestForDiscovery8ed70b09-b4d3-4a5d-9f75-12b13a332204

Files

Original bundle
Now showing 1 - 1 of 1
No Thumbnail Available
Name:
Hexanuclear and undecanuclear iron(III) carboxylates as catalyst precursors for cyclohexane oxidation.rep.pdf
Size:
205.52 KB
Format:
Adobe Portable Document Format
Download
License bundle
Now showing 1 - 1 of 1
No Thumbnail Available
Name:
license.txt
Size:
1.71 KB
Format:
Item-specific license agreed upon to submission
Description:
Download

Collections

ISEL - Eng. Quim. Biol. - Artigos