Publicação
Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols
| Resumo: | A one-pot template reaction of sodium 2-(2-(dicyanomethylene) hydrazinyl) benzenesulfonate (NaHL1) with water and manganese(II) acetate tetrahydrate led to the mononuclear complex [Mn(H2O)(6)](HL1a)(2)center dot 4H(2)O (1), where (HL1a) -= 2-(SO3-)C6H4(NH)=N=C(C N) (CONH2) is the carboxamide species derived from nucleophilic attack of water on a cyano group of (HL1) . The copper tetramer [Cu-4(H2O)(10)(-) (1 kappa N: kappa O-2: kappa O, 2 kappa N: k(O)-L-2)(2)]center dot 2H(2)O (2) was obtained from reaction of Cu(NO3)(2)center dot 2.5H(2)O with sodium 5-(2( 4,4-dimethyl-2,6-dioxocyclohexylidene) hydrazinyl)-4-hydroxybenzene-1,3-disulfonate (Na2H2L2). Both complexes were characterized by elemental analysis, IR spectroscopy, ESI-MS and single crystal X-ray diffraction. They exhibit a high catalytic activity for the solvent-and additive-free microwave (MW) assisted oxidation of primary and secondary alcohols with tert-butylhydroperoxide, leading to yields of the oxidized products up to 85.5% and TOFs up to 1.90 x 103 h(-1) after 1 h under low power (5-10 W) MW irradiation. Moreover, the heterogeneous catalysts are easily recovered and reused, at least for three consecutive cycles, maintaining 89% of the initial activity and a high selectivity. |
|---|---|
| Autores principais: | Mahmudov, Kamran |
| Outros Autores: | Sutradhar, Manas; Martins, Luisa; Silva, Maria de Fátima C. Guedes da; Ribera, Alice; Nunes, Ana V. M.; Gahramanova, Shahnaz; Marchetti, Fabio; Pombeiro, Armando |
| Assunto: | Aerobic oxidation Copper(Ii) complexes Benzylic alcohols Mild conditions Nitroxyl radicals Iron complexes Beta-diketones Ligands Aldehydes Tempo |
| Ano: | 2015 |
| País: | Portugal |
| Tipo de documento: | artigo |
| Tipo de acesso: | acesso restrito |
| Instituição associada: | Instituto Politécnico de Lisboa |
| Idioma: | inglês |
| Origem: | Repositório Científico do Instituto Politécnico de Lisboa |
| _version_ | 1866887376979099648 |
|---|---|
| author | Mahmudov, Kamran |
| author2 | Sutradhar, Manas Martins, Luisa Silva, Maria de Fátima C. Guedes da Ribera, Alice Nunes, Ana V. M. Gahramanova, Shahnaz Marchetti, Fabio Pombeiro, Armando |
| author2_role | author author author author author author author author |
| author_facet | Mahmudov, Kamran Sutradhar, Manas Martins, Luisa Silva, Maria de Fátima C. Guedes da Ribera, Alice Nunes, Ana V. M. Gahramanova, Shahnaz Marchetti, Fabio Pombeiro, Armando |
| author_role | author |
| contributor_name_str_mv | RCIPL |
| country_str | PT |
| creators_json_txt | [{\"Person.name\":\"Mahmudov, Kamran\",\"Person.identifier.orcid\":\"0000-0003-0743-6520\"},{\"Person.name\":\"Sutradhar, Manas\",\"Person.identifier.orcid\":\"0000-0003-3349-9154\"},{\"Person.name\":\"Martins, Luisa\",\"Person.identifier.orcid\":\"0000-0002-5403-9352\"},{\"Person.name\":\"Silva, Maria de Fátima C. Guedes da\"},{\"Person.name\":\"Ribera, Alice\"},{\"Person.name\":\"Nunes, Ana V. M.\"},{\"Person.name\":\"Gahramanova, Shahnaz\",\"Person.identifier.orcid\":\"0000-0001-7955-4118\"},{\"Person.name\":\"Marchetti, Fabio\"},{\"Person.name\":\"Pombeiro, Armando\",\"Person.identifier.orcid\":\"0000-0001-8323-888X\"}] |
| datacite.contributors.contributor.contributorName.fl_str_mv | RCIPL |
| datacite.creators.creator.creatorName.fl_str_mv | Mahmudov, Kamran Sutradhar, Manas Martins, Luisa Silva, Maria de Fátima C. Guedes da Ribera, Alice Nunes, Ana V. M. Gahramanova, Shahnaz Marchetti, Fabio Pombeiro, Armando |
| datacite.date.Accepted.fl_str_mv | 2015-01-01T00:00:00Z |
| datacite.date.available.fl_str_mv | 2016-04-28T12:41:28Z |
| datacite.date.embargoed.fl_str_mv | 2016-04-28T12:41:28Z |
| datacite.rights.fl_str_mv | http://purl.org/coar/access_right/c_16ec |
| datacite.subjects.subject.fl_str_mv | Aerobic oxidation Copper(Ii) complexes Benzylic alcohols Mild conditions Nitroxyl radicals Iron complexes Beta-diketones Ligands Aldehydes Tempo |
| datacite.titles.title.fl_str_mv | Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols |
| dc.contributor.none.fl_str_mv | RCIPL |
| dc.creator.none.fl_str_mv | Mahmudov, Kamran Sutradhar, Manas Martins, Luisa Silva, Maria de Fátima C. Guedes da Ribera, Alice Nunes, Ana V. M. Gahramanova, Shahnaz Marchetti, Fabio Pombeiro, Armando |
| dc.date.Accepted.fl_str_mv | 2015-01-01T00:00:00Z |
| dc.date.available.fl_str_mv | 2016-04-28T12:41:28Z |
| dc.date.embargoed.fl_str_mv | 2016-04-28T12:41:28Z |
| dc.format.none.fl_str_mv | application/pdf |
| dc.identifier.none.fl_str_mv | http://hdl.handle.net/10400.21/6121 |
| dc.language.none.fl_str_mv | eng |
| dc.publisher.none.fl_str_mv | Royal Soc Chemistry |
| dc.rights.none.fl_str_mv | http://purl.org/coar/access_right/c_16ec |
| dc.subject.none.fl_str_mv | Aerobic oxidation Copper(Ii) complexes Benzylic alcohols Mild conditions Nitroxyl radicals Iron complexes Beta-diketones Ligands Aldehydes Tempo |
| dc.title.fl_str_mv | Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols |
| dc.type.none.fl_str_mv | http://purl.org/coar/resource_type/c_6501 |
| description | A one-pot template reaction of sodium 2-(2-(dicyanomethylene) hydrazinyl) benzenesulfonate (NaHL1) with water and manganese(II) acetate tetrahydrate led to the mononuclear complex [Mn(H2O)(6)](HL1a)(2)center dot 4H(2)O (1), where (HL1a) -= 2-(SO3-)C6H4(NH)=N=C(C N) (CONH2) is the carboxamide species derived from nucleophilic attack of water on a cyano group of (HL1) . The copper tetramer [Cu-4(H2O)(10)(-) (1 kappa N: kappa O-2: kappa O, 2 kappa N: k(O)-L-2)(2)]center dot 2H(2)O (2) was obtained from reaction of Cu(NO3)(2)center dot 2.5H(2)O with sodium 5-(2( 4,4-dimethyl-2,6-dioxocyclohexylidene) hydrazinyl)-4-hydroxybenzene-1,3-disulfonate (Na2H2L2). Both complexes were characterized by elemental analysis, IR spectroscopy, ESI-MS and single crystal X-ray diffraction. They exhibit a high catalytic activity for the solvent-and additive-free microwave (MW) assisted oxidation of primary and secondary alcohols with tert-butylhydroperoxide, leading to yields of the oxidized products up to 85.5% and TOFs up to 1.90 x 103 h(-1) after 1 h under low power (5-10 W) MW irradiation. Moreover, the heterogeneous catalysts are easily recovered and reused, at least for three consecutive cycles, maintaining 89% of the initial activity and a high selectivity. |
| dirty | 0 |
| eu_rights_str_mv | restrictedAccess |
| format | article |
| fulltext.url.fl_str_mv | https://repositorio.ipl.pt/bitstreams/4924a66b-3bbe-4747-9c15-5105a9790ea4/download |
| id | ripl_fea77f4ea12203c58dc4384c1944c953 |
| identifier.url.fl_str_mv | http://hdl.handle.net/10400.21/6121 |
| instacron_str | ipl |
| institution | Instituto Politécnico de Lisboa |
| instname_str | Instituto Politécnico de Lisboa |
| language | eng |
| network_acronym_str | ripl |
| network_name_str | Repositório Científico do Instituto Politécnico de Lisboa |
| oai_identifier_str | oai:repositorio.ipl.pt:10400.21/6121 |
| organization_str_mv | urn:organizationAcronym:ipl |
| person_str_mv | Mahmudov, Kamran Mahmudov, Kamran https://www.ciencia-id.pt/CD1F-CB64-9EA5 CD1F-CB64-9EA5 http://orcid.org/0000-0003-0743-6520 0000-0003-0743-6520 Sutradhar, Manas Sutradhar, Manas https://www.ciencia-id.pt/D518-3A34-8E31 D518-3A34-8E31 http://orcid.org/0000-0003-3349-9154 0000-0003-3349-9154 Martins, Luisa Martins, Luisa https://www.ciencia-id.pt/E218-E297-A4EA E218-E297-A4EA http://orcid.org/0000-0002-5403-9352 0000-0002-5403-9352 Silva, Maria de Fátima C. Guedes da Ribera, Alice Nunes, Ana V. M. Gahramanova, Shahnaz Gahramanova, Shahnaz http://orcid.org/0000-0001-7955-4118 0000-0001-7955-4118 Marchetti, Fabio Pombeiro, Armando Pombeiro, Armando https://www.ciencia-id.pt/8311-38FA-CEFB 8311-38FA-CEFB http://orcid.org/0000-0001-8323-888X 0000-0001-8323-888X |
| publishDate | 2015 |
| publisher.none.fl_str_mv | Royal Soc Chemistry |
| reponame_str | Repositório Científico do Instituto Politécnico de Lisboa |
| repository_id_str | urn:repositoryAcronym:ripl |
| service_str_mv | urn:repositoryAcronym:ripl |
| spelling | engRoyal Soc Chemistrypt_PTA one-pot template reaction of sodium 2-(2-(dicyanomethylene) hydrazinyl) benzenesulfonate (NaHL1) with water and manganese(II) acetate tetrahydrate led to the mononuclear complex [Mn(H2O)(6)](HL1a)(2)center dot 4H(2)O (1), where (HL1a) -= 2-(SO3-)C6H4(NH)=N=C(C N) (CONH2) is the carboxamide species derived from nucleophilic attack of water on a cyano group of (HL1) . The copper tetramer [Cu-4(H2O)(10)(-) (1 kappa N: kappa O-2: kappa O, 2 kappa N: k(O)-L-2)(2)]center dot 2H(2)O (2) was obtained from reaction of Cu(NO3)(2)center dot 2.5H(2)O with sodium 5-(2( 4,4-dimethyl-2,6-dioxocyclohexylidene) hydrazinyl)-4-hydroxybenzene-1,3-disulfonate (Na2H2L2). Both complexes were characterized by elemental analysis, IR spectroscopy, ESI-MS and single crystal X-ray diffraction. They exhibit a high catalytic activity for the solvent-and additive-free microwave (MW) assisted oxidation of primary and secondary alcohols with tert-butylhydroperoxide, leading to yields of the oxidized products up to 85.5% and TOFs up to 1.90 x 103 h(-1) after 1 h under low power (5-10 W) MW irradiation. Moreover, the heterogeneous catalysts are easily recovered and reused, at least for three consecutive cycles, maintaining 89% of the initial activity and a high selectivity.application/pdfpt_PTMn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcoholsPersonalMahmudov, KamranDSpacehttp://dspace.org/items/71d8ce81-a614-49c5-8606-e351da465649DSpacehttp://dspace.org/items/71d8ce81-a614-49c5-8606-e351da465649MahmudovKamranCiência IDhttps://www.ciencia-id.ptCD1F-CB64-9EA5ORCIDhttp://orcid.org0000-0003-0743-6520Researcher IDhttps://www.researcherid.comI-1409-2013Scopus Author IDhttps://www.scopus.com24468352000PersonalSutradhar, ManasDSpacehttp://dspace.org/items/bc59e87c-129a-4038-9eb1-69fbe6753b98DSpacehttp://dspace.org/items/bc59e87c-129a-4038-9eb1-69fbe6753b98SutradharManasCiência IDhttps://www.ciencia-id.ptD518-3A34-8E31ORCIDhttp://orcid.org0000-0003-3349-9154Researcher IDhttps://www.researcherid.comM-4089-2013Scopus Author IDhttps://www.scopus.com14053084900PersonalMartins, LuisaDSpacehttp://dspace.org/items/8ed70b09-b4d3-4a5d-9f75-12b13a332204DSpacehttp://dspace.org/items/8ed70b09-b4d3-4a5d-9f75-12b13a332204MartinsLuisaCiência IDhttps://www.ciencia-id.ptE218-E297-A4EAORCIDhttp://orcid.org0000-0002-5403-9352Researcher IDhttps://www.researcherid.comG-6210-2011Scopus Author IDhttps://www.scopus.com8650947800Silva, Maria de Fátima C. Guedes daRibera, AliceNunes, Ana V. M.PersonalGahramanova, ShahnazDSpacehttp://dspace.org/items/7750d229-4e6d-4d05-a728-f411b1bf355eDSpacehttp://dspace.org/items/7750d229-4e6d-4d05-a728-f411b1bf355eGahramanovaShahnazORCIDhttp://orcid.org0000-0001-7955-4118Researcher IDhttps://www.researcherid.comN-4706-2018Scopus Author IDhttps://www.scopus.com56897125600Marchetti, FabioPersonalPombeiro, ArmandoDSpacehttp://dspace.org/items/6d18ff2e-5c33-4010-b1e7-964c72349813DSpacehttp://dspace.org/items/6d18ff2e-5c33-4010-b1e7-964c72349813PombeiroArmandoCiência IDhttps://www.ciencia-id.pt8311-38FA-CEFBORCIDhttp://orcid.org0000-0001-8323-888XResearcher IDhttps://www.researcherid.comI-5945-2012Scopus Author IDhttps://www.scopus.com7006067269HostingInstitutionOrganizationalRCIPLe-mailmailto:rcaap@sp.ipl.ptrcaap@sp.ipl.ptISSNIsPartOf2046-2069DOIIsPartOf10.1039/C5RA02667A2016-04-28T12:41:28Z20152015-01-01T00:00:00ZHandlehttp://hdl.handle.net/10400.21/6121http://purl.org/coar/access_right/c_16ecrestricted accessAerobic oxidationCopper(Ii) complexesBenzylic alcoholsMild conditionsNitroxyl radicalsIron complexesBeta-diketonesLigandsAldehydesTempo1278252 bytesliteraturehttp://purl.org/coar/resource_type/c_6501journal articlehttp://purl.org/coar/access_right/c_16ecapplication/pdffulltexthttps://repositorio.ipl.pt/bitstreams/4924a66b-3bbe-4747-9c15-5105a9790ea4/downloadRSC Advances5332597925987 |
| spellingShingle | Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols Mahmudov, Kamran Aerobic oxidation Copper(Ii) complexes Benzylic alcohols Mild conditions Nitroxyl radicals Iron complexes Beta-diketones Ligands Aldehydes Tempo |
| status | SINGLETON |
| subject.fl_str_mv | Aerobic oxidation Copper(Ii) complexes Benzylic alcohols Mild conditions Nitroxyl radicals Iron complexes Beta-diketones Ligands Aldehydes Tempo |
| title | Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols |
| title_full | Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols |
| title_fullStr | Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols |
| title_full_unstemmed | Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols |
| title_short | Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols |
| title_sort | Mn-II and Cu-II complexes with arylhydrazones of active methylene compounds as effective heterogeneous catalysts for solvent- and additive-free microwave-assisted peroxidative oxidation of alcohols |
| topic | Aerobic oxidation Copper(Ii) complexes Benzylic alcohols Mild conditions Nitroxyl radicals Iron complexes Beta-diketones Ligands Aldehydes Tempo |
| topic_facet | Aerobic oxidation Copper(Ii) complexes Benzylic alcohols Mild conditions Nitroxyl radicals Iron complexes Beta-diketones Ligands Aldehydes Tempo |
| url | http://hdl.handle.net/10400.21/6121 |
| visible | 1 |