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Synthesis and catalytic properties in olefin epoxidation of octahedral dichloridodioxidomolybdenum(VI) complexes bearing N,N-dialkylamide ligands: crystal structure of [Mo2O4(mu(2)-O)Cl-2(dmf)(4)]

2009Journal article Restricted access
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dc.contributor.authorGago, Sandra
dc.contributor.authorNeves, Patrícia
dc.contributor.authorMonteiro, Bernardo
dc.contributor.authorPessêgo, Márcia
dc.contributor.authorLopes, Andre D.
dc.contributor.authorValente, Anabela A.
dc.contributor.authorAlmeida Paz, Filipe A.
dc.contributor.authorPillinger, Martyn
dc.contributor.authorMoreira, José
dc.contributor.authorSilva, Carlos M.
dc.contributor.authorGonçalves, Isabel S.
dc.date.accessioned2013-12-06T15:42:35Z
dc.date.available2013-12-06T15:42:35Z
dc.date.issued2009
dc.date.updated2013-12-04T18:14:36Z
dc.description.abstractThe catalytic performance of the complexes [MoO2Cl2(L)2][L = N,N-dimethylformamide (dmf), N,N-dimethylacetamide(dma), N,N-dimethylpropionamide (dmpa), N,N-diethylformamide(def) and N,N-diphenylformamide (dpf)] was examined in the epoxidation of cis-cyclooctene with tert-butyl hydroperoxide(tbhp) at 55 °C and in the absence of a cosolvent.The complexes showed high turnover frequencies in the range of 561–577 molmolMo–1h–1, giving the epoxide as the only product in 98% yield after 6 h. The reaction rates decreased significantly in consecutive runs carried out by recharging the reactors with olefin and oxidant. On the basis of the IR spectroscopic characterisation of the solids recovered at the end of the catalytic reactions, the decrease in activity is attributed to the formation of dioxido(μ-oxido)-molybdenum(VI) dimers. Accordingly, the treatment of [MoO2Cl2(dmf)2] with an excess amount of tbhp led to the isolation of [Mo2O4(μ2-O)Cl2(dmf)4], which was characterised by single-crystal X-ray diffraction and found to exhibit a catalytic performance very similar to that found in the second runs for the mononuclear complexes. The kinetics of the reaction of [MoO2Cl2(dmf)2] with tbhp was further examined by UV/Vis spectroscopy, allowing rate constants and activation parameters to be determined. For the dpf adduct, the effect of different solvents on cyclooctene epoxidation and the epoxidation of other olefins, namely, (R)-(+)-limonene, α-pinene and norbornene, were investigatedpor
dc.identifier.citationGago, Sandra; Neves, Patrícia; Monteiro, Bernardo; Pessêgo, Márcia; Lopes, André D.; Valente, Anabela A.; Almeida Paz, Filipe A.; Pillinger, Martyn; Moreira, José A.; Silva, Carlos M.; Gonçalves, Isabel S.Synthesis and Catalytic Properties in Olefin Epoxidation of Octahedral Dichloridodioxidomolybdenum(VI) Complexes Bearing N,N-Dialkylamide Ligands: Crystal Structure of [Mo2O4(mu(2)-O)Cl-2(dmf)(4)], European Journal of Inorganic Chemistry, 2009, 29-30, 4528-4537, 2009.por
dc.identifier.doihttp://dx.doi.org/10.1002/ejic.200900544
dc.identifier.issn1434-1948
dc.identifier.otherAUT: JMO01545; ADL01681;
dc.identifier.urihttp://hdl.handle.net/10400.1/3227
dc.language.isoengpor
dc.peerreviewedyespor
dc.publisherWiley-VCH Verlagpor
dc.subjectMolybdenumpor
dc.subjectO ligandspor
dc.subjectHomogeneous catalysispor
dc.subjectEpoxidationpor
dc.subjectKineticspor
dc.titleSynthesis and catalytic properties in olefin epoxidation of octahedral dichloridodioxidomolybdenum(VI) complexes bearing N,N-dialkylamide ligands: crystal structure of [Mo2O4(mu(2)-O)Cl-2(dmf)(4)]por
dc.typejournal article
dspace.entity.typePublication
oaire.citation.endPage4537por
oaire.citation.issue29-30
oaire.citation.startPage4528por
oaire.citation.titleEuropean Journal of Inorganic Chemistrypor
oaire.citation.volume2009por
person.familyNameD. Lopes
person.familyNameMoreira
person.givenNameAndré
person.givenNameJosé
person.identifier2824636
person.identifier.ciencia-id351E-856A-0300
person.identifier.ciencia-idDC11-4E1F-F13F
person.identifier.orcid0000-0002-9702-1216
person.identifier.orcid0000-0001-8481-3436
person.identifier.ridE-2136-2012
person.identifier.ridF-3807-2010
person.identifier.scopus-author-id7201958625
person.identifier.scopus-author-id7201506886
rcaap.rightsrestrictedAccesspor
rcaap.typearticlepor
relation.isAuthorOfPublicationf2f0fe56-e04d-4229-b37b-2b9f1789fe2d
relation.isAuthorOfPublication644799ac-df06-4840-9f12-52c5b3ff0a76
relation.isAuthorOfPublication.latestForDiscovery644799ac-df06-4840-9f12-52c5b3ff0a76

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