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Chemistry and catalytic performance of pyridyl-benzimidazole oxidomolybdenum(VI) compounds in (bio)olefin epoxidation

2017-05Journal article Restricted access
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dc.contributor.authorNeves, Patricia
dc.contributor.authorNogueira, Lucie S.
dc.contributor.authorGomes, Ana C.
dc.contributor.authorOliveira, Tânia S. M.
dc.contributor.authorLopes, Andre D.
dc.contributor.authorValente, Anabela A.
dc.contributor.authorGonçalves, Isabel S.
dc.contributor.authorPillinger, Martyn
dc.date.accessioned2019-11-20T15:07:36Z
dc.date.available2019-11-20T15:07:36Z
dc.date.issued2017-05
dc.description.abstractThe chemistry and catalytic performance of the dichlorido complex [MoO2Cl2(pbim)] (1) [pbim = 2-(2-pyridyl)benzimidazole] in the epoxidation of olefins is reported. Complex 1 acts as a precatalyst and is more effective with tert-butyl-hydroperoxide (TBHP) as the oxidant than with aq. hydrogen peroxide: the cis-cyclooctene (Cy) reaction with TBHP gave 98 % epoxide yield at 70 degrees C/24 h. Catalyst characterization showed that 1 is transformed in situ to the oxidodiperoxido complex [MoO(O-2)(2)(pbim)] (2), with H2O2 and a hybrid molybdenum(VI) oxide solid formulated as [MoO3(pbim)] (3) with TBHP. The hybrid material 3 was prepared on a larger scale and explored for the epoxidation of the biorenewable olefins methyl oleate, methyl linoleate, and (R)-(+)-limonene. With TBHP as the oxidant, 3 acts as a source of soluble active species of the type 2. A practical method for recycling oxidodiperoxidomolybdenum(VI) catalysts for the Cy/TBHP reaction is demonstrated by using an ionic liquid as the solvent for the molecular catalyst 2.
dc.description.sponsorshipNational funds through the Fundacao para a Ciencia e a Tecnologia (FCT) [POCI-01-0145-FEDER-007679, PD/BD/109666/2015]
dc.description.sponsorshipMinisterio da Educacao e Ciencia (MEC)
dc.description.sponsorshipFundo Europeu de Desenvolvimento Regional (FEDER)
dc.description.sponsorshipEuropean Union [PD/BD/109666/2015, SFRH/BPD/110530/2015, SFRH/BPD/108541/2015]
dc.description.sponsorshipMinisterio da Ciencia, Tecnologia e Ensino Superior (MCTES)
dc.description.sponsorshipEuropean Social Fund through the program Programa Operacional Potencial Humano (POPH) of Quadro de Referencia Estrategica Nacional (QREN)
dc.description.versioninfo:eu-repo/semantics/publishedVersion
dc.identifier.doi10.1002/ejic.201700286
dc.identifier.issn1434-1948
dc.identifier.issn1099-0682
dc.identifier.urihttp://hdl.handle.net/10400.1/13121
dc.language.isoeng
dc.peerreviewedyes
dc.publisherWiley-VCH Verlag
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.subjectOxo-molybdenum complexes
dc.subjectMetal-organic framework
dc.subjectStructural elucidation
dc.subjectEfficient catalysts
dc.subjectDioxomolybdenum(Vi)-bpyridine complexes
dc.subjectHydrothermal synthesis
dc.subjectRhenium complexes
dc.subjectPeroxo complexes
dc.subjectDioxo complexes
dc.titleChemistry and catalytic performance of pyridyl-benzimidazole oxidomolybdenum(VI) compounds in (bio)olefin epoxidation
dc.typejournal article
dspace.entity.typePublication
oaire.awardURIinfo:eu-repo/grantAgreement/FCT/5876/UID%2FCTM%2F50011%2F2013/PT
oaire.citation.endPage2627
oaire.citation.issue19
oaire.citation.startPage2617
oaire.citation.titleEuropean Journal of Inorganic Chemistry
oaire.fundingStream5876
person.familyNameD. Lopes
person.givenNameAndré
person.identifier2824636
person.identifier.ciencia-id351E-856A-0300
person.identifier.orcid0000-0002-9702-1216
person.identifier.ridE-2136-2012
person.identifier.scopus-author-id7201958625
project.funder.identifierhttp://doi.org/10.13039/501100001871
project.funder.nameFundação para a Ciência e a Tecnologia
rcaap.rightsrestrictedAccess
rcaap.typearticle
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