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Cooperative metal–ligand Assisted E/Z isomerization and cyano activation at CuII and CoII complexes of arylhydrazones of active methylene nitriles

2014-08Journal article Restricted access
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dc.contributor.authorMahmudov, Kamran
dc.contributor.authorKopylovich, Maximilian N.
dc.contributor.authorSABBATINI, Alessandra
dc.contributor.authorDrew, Michael G. B.
dc.contributor.authorMartins, Luisa
dc.contributor.authorPettinari, Claudio
dc.contributor.authorPombeiro, Armando
dc.date.accessioned2018-02-28T10:23:08Z
dc.date.available2018-02-28T10:23:08Z
dc.date.issued2014-08
dc.description.abstractNew (E/Z)-2-(2-(1-cyano-2-methoxy-2-oxoethylidene)hydrazinyl)benzoic acid (H2L4) and known sodium 2-(2-(dicyanomethylene)hydrazinyl)benzenesulfonate (NaHL1), 2-(2-(dicyano-methylene)hydrazinyl)benzoic acid (H2L2), and sodium (E/Z)-2-(2-(1-cyano-2-methoxy-2-oxoethylidene)hydrazinyl)benzenesulfonate (NaHL3) were used in the template synthesis of a series of CuII and CoII complexes [Cu(H2O)2L1a]·H2O (1), [Cu(H2O)(3-pyon)L1b]·H2O (2), [Cu(H2O)(4-pyon)L1b] (3), [Co(H2O)-((CH3)2NCHO)(μ-L2a)]2·(CH3)2NCHO (4), [Cu3(μ3-OH)-(NO3)(CH3OH)(μ2-X)3(μ2-HL3)] (5), [Cu(H2O)(py)L3]·H2O (6), [Cu(H2O)2(μ-L4)]6 ·6H2O (7), [Cu(2-cnpyb)2(L1b)2]·2H2O (8), [Cu(2-cnpya)2(L1a)2]·2H2O (9), and [Cu(H2O)(4-cnpy)(L1a)2] (10), where 3-pyon = 1-(pyridin-3-yl)ethanone, 4-pyon = 1-(pyridin-4-yl)ethanone, py = pyridine, HX = syn-2-pyridinealdoxime, 4-cnpy = 4-cyanopyridine; 2-cnpya, 2-cnpyb, L1a, L1b, L2a are the ligands derived from nucleophilic attack of methanol (a) or water (b) on a cyano group of 2-cyanopyridine (2-cnpy), L1 or L2, respectively, giving the corresponding iminoesters (2-cnpya, L1a or L2a) or carboxamides (2-cnpyb or L1b). An auxiliary ligand, namely syn-2-pyridinealdoxime or pyridine, acting cooperatively with the metal ion (CuII in this case), induced an E/Z isomerization of the H2L4 ligand; the E- and Z-isomers were isolated separately and fully characterized (compounds 9 and 10, respectively). A one-pot activation of nitrile groups in different molecules was achieved in the syntheses of 8 and 9. Complexes 1−10 are catalyst precursors for the solvent-free microwave (MW)-assisted selective oxidation of secondary alcohols to the corresponding ketones, with typical yields in the 29−99% range (TOFs up to 4.94 × 103 h−1) after 30 min of MW irradiation.pt_PT
dc.description.versioninfo:eu-repo/semantics/publishedVersionpt_PT
dc.identifier.citationMAHMUDOV, Kamran T.; [et al] – Cooperative metal–ligand Assisted E/Z isomerization and cyano activation at CuII and CoII complexes of arylhydrazones of active methylene nitriles. Inorganic Chemistry. ISSN 0220-1669. Vol. 53, N.º 18, (2014), pp. 9946-9958.pt_PT
dc.identifier.doi10.1021/ic501704gpt_PT
dc.identifier.issn0220-1669
dc.identifier.issn1520-510X
dc.identifier.urihttp://hdl.handle.net/10400.21/8151
dc.language.isoengpt_PT
dc.peerreviewedyespt_PT
dc.publisherAmerican Chemical Societypt_PT
dc.relation.publisherversionhttps://pubs.acs.org/doi/pdf/10.1021/ic501704gpt_PT
dc.subjectNitrilept_PT
dc.subjectNucleophilicpt_PT
dc.titleCooperative metal–ligand Assisted E/Z isomerization and cyano activation at CuII and CoII complexes of arylhydrazones of active methylene nitrilespt_PT
dc.typejournal article
dspace.entity.typePublication
oaire.awardURIinfo:eu-repo/grantAgreement/FCT/3599-PPCDT/PEst-OE%2FQUI%2FUI0100%2F2013/PT
oaire.citation.endPage9958pt_PT
oaire.citation.issue18pt_PT
oaire.citation.startPage9946pt_PT
oaire.citation.titleInorganic Chemistrypt_PT
oaire.citation.volume53pt_PT
oaire.fundingStream3599-PPCDT
person.familyNameMahmudov
person.familyNameKopylovich
person.familyNameSABBATINI
person.familyNameMartins
person.familyNamePettinari
person.familyNamePombeiro
person.givenNameKamran
person.givenNameMaximilian
person.givenNameAlessandra
person.givenNameLuisa
person.givenNameClaudio
person.givenNameArmando
person.identifier637885
person.identifier.ciencia-idCD1F-CB64-9EA5
person.identifier.ciencia-idE416-945D-A277
person.identifier.ciencia-idE218-E297-A4EA
person.identifier.ciencia-id8311-38FA-CEFB
person.identifier.orcid0000-0003-0743-6520
person.identifier.orcid0000-0002-6307-327X
person.identifier.orcid0000-0002-2906-162X
person.identifier.orcid0000-0002-5403-9352
person.identifier.orcid0000-0002-2547-7206
person.identifier.orcid0000-0001-8323-888X
person.identifier.ridI-1409-2013
person.identifier.ridH-8625-2012
person.identifier.ridG-6210-2011
person.identifier.ridI-5945-2012
person.identifier.scopus-author-id24468352000
person.identifier.scopus-author-id7003887561
person.identifier.scopus-author-id8650947800
person.identifier.scopus-author-id7006581579
person.identifier.scopus-author-id7006067269
project.funder.identifierhttp://doi.org/10.13039/501100001871
project.funder.nameFundação para a Ciência e a Tecnologia
rcaap.rightsclosedAccesspt_PT
rcaap.typearticlept_PT
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