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Oxorhenium complexes bearing the water-soluble tris(pyrazol-1-yl)methanesulfonate, 1,3,5-triaza-7-phosphaadamantane, or related ligands, as catalysts for baeyer-villiger oxidation of ketones

2013-04-15Journal article Open access
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dc.contributor.authorMartins, Luisa
dc.contributor.authorAlegria, Elisabete
dc.contributor.authorSmolenski, Piotr
dc.contributor.authorKuznetsov, Maxim L.
dc.contributor.authorPombeiro, Armando
dc.date.accessioned2013-11-05T19:27:34Z
dc.date.available2013-11-05T19:27:34Z
dc.date.issued2013-04-15
dc.description.abstractNew rhenium(VII or III) complexes [ReO3(PTA)(2)][ReO4] (1) (PTA = 1,3,5-triaza-7-phosphaadamantane), [ReO3(mPTA)][ReO4] (2) (mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane cation), [ReO3(HMT)(2)] [ReO4] (3) (HMT = hexamethylenetetramine), [ReO3(eta(2)-Tpm)(PTA)][ReO4] (4) [Tpm = hydrotris(pyrazol-1-yl)methane, HC(pz)(3), pz = pyrazolyl), [ReO3(Hpz)(HMT)][ReO4] (5) (Hpz = pyrazole), [ReO(Tpms)(HMT)] (6) [Tpms = tris(pyrazol-1-yl)methanesulfonate, O3SC(pz)(3)(-)] and [ReCl2{N2C(O)Ph} (PTA)(3)] (7) have been prepared from the Re(VII) oxide Re2O2 (1-6) or, in the case of 7, by ligand exchange from the benzoyldiazenido complex [ReCl2(N2C-(O)Ph}(Hpz)(PPh3)(2)], and characterized by IR and NMR spectroscopies, elemental analysis and electrochemical properties. Theoretical calculations at the density functional theory (DFT) level of theory indicated that the coordination of PTA to both Re(III) and Re(VII) centers by the P atom is preferable compared to the coordination by the N atom. This is interpreted in terms of the Re-PTA bond energy and hard-soft acid-base theory. The oxo-rhenium complexes 1-6 act as selective catalysts for the Baeyer-Villiger oxidation of cyclic and linear ketones (e.g., 2-methylcyclohexanone, 2-methylcyclopentanone, cyclohexanone, cyclopentanone, cyclobutanone, and 3,3-dimethyl-2-butanone or pinacolone) to the corresponding lactones or esters, in the presence of aqueous H2O2. The effects of a variety of factors are studied toward the optimization of the process.por
dc.identifier.citationMARTINS, Luisa M. D. R. S.; ALEGRIA, Elisabete C. B. A.; SMOLENSKI, Piotr; KUZNETSOV, Maxim L.; POMBEIRO, Armando J. L. - Oxorhenium complexes bearing the water-soluble tris(pyrazol-1-yl)methanesulfonate, 1,3,5-triaza-7-phosphaadamantane, or related ligands, as catalysts for baeyer-villiger oxidation of ketones. Inorganic Chemistry. ISSN 0020-1669. Vol. 52, nr. 8 (2013), p. 4534-4546.por
dc.identifier.issn0020-1669
dc.identifier.other10.1021/ic400024r
dc.identifier.urihttp://hdl.handle.net/10400.21/2870
dc.language.isoengpor
dc.peerreviewedyespor
dc.publisherAmer Chemical SOCpor
dc.subjectRay Crystal-structurespor
dc.subjectTransition-metal-complexespor
dc.subjectHydrogen-peroxidepor
dc.subjectRhenium complexespor
dc.subjectOrganometallic compoundspor
dc.subjectCoordination chemistrypor
dc.subjectMolecular-oxygenpor
dc.subjectMild conditionspor
dc.subjectIonic liquidspor
dc.subjectStructural-characterizationpor
dc.titleOxorhenium complexes bearing the water-soluble tris(pyrazol-1-yl)methanesulfonate, 1,3,5-triaza-7-phosphaadamantane, or related ligands, as catalysts for baeyer-villiger oxidation of ketonespor
dc.typejournal article
dspace.entity.typePublication
oaire.citation.conferencePlaceWashingtonpor
oaire.citation.endPage4546por
oaire.citation.issue8por
oaire.citation.startPage4534por
oaire.citation.titleInorganic Chemistrypor
oaire.citation.volume52por
person.familyNameMartins
person.familyNameAlegria
person.familyNameSmolenski
person.familyNameKuznetsov
person.familyNamePombeiro
person.givenNameLuisa
person.givenNameElisabete
person.givenNamePiotr
person.givenNameMaxim L.
person.givenNameArmando
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person.identifier863202
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person.identifier.orcid0000-0002-5403-9352
person.identifier.orcid0000-0003-4060-1057
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person.identifier.orcid0000-0001-8323-888X
person.identifier.ridG-6210-2011
person.identifier.ridE-9945-2012
person.identifier.ridH-7934-2012
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person.identifier.scopus-author-id8650947800
person.identifier.scopus-author-id8315848300
person.identifier.scopus-author-id23091814400
person.identifier.scopus-author-id7102379353
person.identifier.scopus-author-id7006067269
rcaap.rightsrestrictedAccesspor
rcaap.typearticlepor
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