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Bis(pyrazolyl)methanetetracarbonyl-molybdenum(0) as precursor to a molybdenum(VI) catalyst for olefin epoxidation

2013Journal article Restricted access
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dc.contributor.authorFigueiredo, Sónia
dc.contributor.authorGomes, Ana C.
dc.contributor.authorFernandes, José A.
dc.contributor.authorPaz, Filipe A. Almeida
dc.contributor.authorLopes, Andre D.
dc.contributor.authorLourenço, J. P.
dc.contributor.authorPillinger, Martyn
dc.contributor.authorGonçalves, Isabel S.
dc.date.accessioned2013-02-19T14:35:05Z
dc.date.available2013-02-19T14:35:05Z
dc.date.issued2013
dc.date.updated2013-02-18T16:54:16Z
dc.description.abstractBis(pyrazolyl)methanetetracarbonyl-molybdenum(0), cis-[Mo(CO)4(BPM)] (1), was prepared from Mo(CO)6 and the ligand bis(pyrazolyl)methane (BPM), and examined as a catalyst precursor for the epoxidation of olefins using tert-butylhydroperoxide (TBHP) as oxidant. Catalytic activities followed the sequence 1-octene < trans-2-octene < a-pinene < (R)-(þ)-limonene < cis-cyclooctene, and, with the exception of a-pinene and limonene, the corresponding epoxide was always the only reaction product. Turnover frequencies for the epoxidation of cyclooctene were 580 mol molMo 1 h 1 at 55 C and 1175 mol molMo 1 h 1 at 75 C, which compare favourably with those found for other molybdenum carbonyl complexes used as catalyst precursors for the same reaction under similar conditions. Catalytic activities were lower in the presence of organic co-solvents, decreasing in the sequence 1,2-dichloroethane > nitromethane > ethanol > hexane > acetonitrile. It is proposed that the oxodiperoxo complex [MoO(O2)2(BPM)] (2) may be the active catalyst formed in situ by oxidative decarbonylation of 1, since crystals of 2 suitable for structure determination by X-ray diffraction were obtained from the reaction solution recovered after a catalytic run at 55 C with cis-cyclooctene as substrate. In support of this hypothesis, the catalytic performance of 2 for the epoxidation of cyclooctene at 55 C is very similar to that for 1.por
dc.identifier.citationFigueiredo, Sónia; Gomes, Ana C.; Fernandes, José A.; Paz, Filipe A. Almeida; Lopes, André D.; Lourenço, João P.; Pillinger, Martyn; Gonçalves, Isabel S.Bis(pyrazolyl)methanetetracarbonyl-molybdenum(0) as precursor to a molybdenum(VI) catalyst for olefin epoxidation, Journal of Organometallic Chemistry, 723, n/a, 56-64, 2013.por
dc.identifier.issn0022-328X
dc.identifier.otherAUT: JLO01215; ADL01681;
dc.identifier.urihttp://hdl.handle.net/10400.1/2367
dc.language.isoengpor
dc.peerreviewedyespor
dc.publisherElsevierpor
dc.subjectCatalytic activitypor
dc.subjectMolybdenumpor
dc.subjectBis(azolyl)methane ligandspor
dc.subjectTetracarbonyl complexespor
dc.subjectOxidative decarbonylationpor
dc.subjectOlefin epoxidationpor
dc.titleBis(pyrazolyl)methanetetracarbonyl-molybdenum(0) as precursor to a molybdenum(VI) catalyst for olefin epoxidationpor
dc.typejournal article
dspace.entity.typePublication
oaire.awardURIinfo:eu-repo/grantAgreement/FCT/COMPETE/PEst-C%2FCTM%2FLA0011%2F2013/PT
oaire.citation.endPage64por
oaire.citation.startPage56por
oaire.citation.titleJournal of Organometallic Chemistrypor
oaire.citation.volume723por
oaire.fundingStreamCOMPETE
person.familyNameD. Lopes
person.familyNameLourenço
person.givenNameAndré
person.givenNameJoão P.
person.identifier2824636
person.identifier634248
person.identifier.ciencia-id351E-856A-0300
person.identifier.ciencia-idF81F-A1F0-2A7C
person.identifier.orcid0000-0002-9702-1216
person.identifier.orcid0000-0002-0501-6672
person.identifier.ridE-2136-2012
person.identifier.ridA-7758-2008
person.identifier.scopus-author-id7201958625
person.identifier.scopus-author-id57195730600
project.funder.identifierhttp://doi.org/10.13039/501100001871
project.funder.nameFundação para a Ciência e a Tecnologia
rcaap.rightsrestrictedAccesspor
rcaap.typearticlepor
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relation.isAuthorOfPublication.latestForDiscoveryf2f0fe56-e04d-4229-b37b-2b9f1789fe2d
relation.isProjectOfPublicationd960b631-c7a8-4eb2-8a24-09e10fef0993
relation.isProjectOfPublication.latestForDiscoveryd960b631-c7a8-4eb2-8a24-09e10fef0993

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