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dc.contributor.authorDas, Biswanath
dc.contributor.authorAl-Hunaiti, Afnan
dc.contributor.authorSánchez-Eguía, Brenda N.
dc.contributor.authorZeglio, Erica
dc.contributor.authorDemeshko, Serhiy
dc.contributor.authorDechert, Sebastian
dc.contributor.authorBraunger, Steffen
dc.contributor.authorHaukka, Matti
dc.contributor.authorRepo, Timo
dc.contributor.authorCastillo, Ivan
dc.contributor.authorNordlander, Ebbe
dc.date.accessioned2019-04-08T09:26:04Z
dc.date.available2019-04-08T09:26:04Z
dc.date.issued2019fi
dc.identifier.citationDas, B., Al-Hunaiti, A., Sánchez-Eguía, B. N., Zeglio, E., Demeshko, S., Dechert, S., . . . Nordlander, E. (2019). Di- and Tetrairon(III) μ-Oxido Complexes of an N3S-Donor Ligand : Catalyst Precursors for Alkene Oxidations. <em>Frontiers in Chemistry</em>, 7, 97. <a href="https://doi.org/10.3389/fchem.2019.00097">doi:10.3389/fchem.2019.00097</a>fi
dc.identifier.otherTUTKAID_81021
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/63427
dc.description.abstractThe new di- and tetranuclear Fe(III) µ-oxido complexes [Fe4(µ-O)4(PTEBIA)4](CF3SO3)4(CH3CN)2] (1a), [Fe2(µ-O)Cl2(PTEBIA)2](CF3SO3)2 (1b), and [Fe2(µ-O)(HCOO)2(PTEBIA)2](ClO4)2 (MeOH) (2) were prepared from the sulfur-containing ligand (2-((2,4-dimethylphenyl)thio)-N,N-bis ((1-methyl-benzimidazol-2-yl)methyl)ethanamine (PTEBIA). The tetrairon complex 1a features four µ-oxido bridges, while in dinuclear 1b, the sulfur moiety of the ligand occupies one of the six coordination sites of each Fe(III) ion with a long Fe-S distance of 2.814(6) Å. In 2, two Fe(III) centers are bridged by one oxido and two formate units, the latter likely formed by methanol oxidation. Complexes 1a and 1b show broad sulfur-toiron charge transfer bands around 400–430 nm at room temperature, consistent with mononuclear structures featuring Fe-S interactions. In contrast, acetonitrile solutions of 2 display a sulfur-to-iron charge transfer band only at low temperature (228 K) upon addition of H2O2/CH3COOH, with an absorption maximum at 410 nm. Homogeneous oxidative catalytic activity was observed for 1a and 1b using H2O2 as oxidant, but with low product selectivity. High valent iron-oxo intermediates could not be detected by UV-vis spectroscopy or ESI mass spectrometry. Rather, evidence suggest preferential ligand oxidation, in line with the relatively low selectivity and catalytic activity observed in the reactions.fi
dc.format.mimetypeapplication/pdf
dc.language.isoeng
dc.publisherFrontiers Media
dc.relation.ispartofseriesFrontiers in Chemistry
dc.rightsCC BY 4.0
dc.subject.otherkompleksiyhdisteetfi
dc.subject.otherrautafi
dc.subject.othereetteritfi
dc.subject.otherhapettuminenfi
dc.subject.otherkatalyysifi
dc.subject.otherFe-S interactionfi
dc.subject.otheroxidationfi
dc.subject.otherhomogeneous catalysisfi
dc.subject.otherthioetherfi
dc.subject.otheriron-oxo complexfi
dc.titleDi- and Tetrairon(III) μ-Oxido Complexes of an N3S-Donor Ligand : Catalyst Precursors for Alkene Oxidationsfi
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-201903201921
dc.contributor.laitosKemian laitosfi
dc.contributor.laitosDepartment of Chemistryen
dc.contributor.oppiaineEpäorgaaninen ja analyyttinen kemia
dc.type.urihttp://purl.org/eprint/type/JournalArticle
dc.date.updated2019-03-20T13:15:41Z
dc.description.reviewstatuspeerReviewed
dc.relation.issn2296-2646
dc.relation.numberinseries0
dc.relation.volume7
dc.type.versionpublishedVersion
dc.rights.copyright© 2019 The Authors.
dc.rights.accesslevelopenAccessfi
dc.format.contentfulltext
dc.rights.urlhttps://creativecommons.org/licenses/by/4.0/
dc.relation.doi10.3389/fchem.2019.00097


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