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dc.contributor.authorSamanta, Subhas
dc.contributor.authorAdak, Laksmikanta
dc.contributor.authorJana, Ranjan
dc.contributor.authorMostafa, Golam
dc.contributor.authorTuononen, Heikki
dc.contributor.authorRanu, Brindaban
dc.contributor.authorGoswami, Sreebrata
dc.date.accessioned2015-11-25T07:13:55Z
dc.date.available2015-11-25T07:13:55Z
dc.date.issued2008
dc.identifier.citationSamanta, S., Adak, L., Jana, R., Mostafa, G., Tuononen, H., Ranu, B., & Goswami, S. (2008). Oxidative ortho-C-N Fusion of Aniline by OsO4. Isolation, Characterization of Oxo-Amido Osmium(VI) Complexes, and their Catalytic Activities for Oxidative C−C Bond Cleavage of Unsaturated Hydrocarbons. <i>Inorganic Chemistry</i>, <i>47</i>(23), 11062-11070. <a href="https://doi.org/10.1021/ic801352d" target="_blank">https://doi.org/10.1021/ic801352d</a>
dc.identifier.otherCONVID_18408227
dc.identifier.otherTUTKAID_33809
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/47809
dc.description.abstractIn an unusual reaction of osmium(VIII) oxide with p-substituted aromatic amines (X-C6H4-NH2, where X = Me, H, Cl) in heptane afforded the brown osmium(VI)-oxo complexes [OsO(L)2] (1a-c, L = N-aryl-1,2-arylenediamide) in moderate yields. The ligand L is formed in situ via oxidative ortho-C-N fusion of arylamines. The reaction occurs in an inert atmosphere, and a part of Os(VIII) is used up for the oxidation of aromatic amine. Single crystal X-ray structure of a representative complex 1a is solved. The structural analysis has authenticated the ortho-C-N fusion of ArNH2 resulting in formation of the diamide ligand, L. The complex as a whole is penta-coordinated, and the coordination sphere has a distorted square pyramidal geometry (τ = 0.26). A similar reaction of osmium(VIII) oxide with the preformed N-phenyl-1,2-phenelene diamine produced the complex 1a in nearly quantitative yield. The substituted phenazine, 5-phenyl-3-phenylimino-3,5-dihydro-phenazine-2-ylamine, is obtained as a byproduct of the latter reaction. The complexes, 1a-c, can be reduced in a reversible one-electron step, as probed by cyclic voltammetry. The one electron reduced paramagnetic Os(V) intermediate is, however, Electron Paramagnetic Resonance (EPR) silent. Solution spectra of the osmium complexes show several multiple transitions in the UV−vis region. Density functional theory calculations were employed to confirm the structural features and to support the spectroscopic assignments. The complex 1a catalyzes oxidation of a wide variety of unsaturated hydrocarbons like alkenes, alkynes, and aldehydes to the corresponding carboxylic acids in the presence of tert-butylhydroperoxide (TBHP) efficiently at room temperature.
dc.language.isoeng
dc.publisherACS
dc.relation.ispartofseriesInorganic Chemistry
dc.subject.otherosmium(VI) kompleksit
dc.subject.otherosmium(VI) complexes
dc.titleOxidative ortho-C-N Fusion of Aniline by OsO4. Isolation, Characterization of Oxo-Amido Osmium(VI) Complexes, and their Catalytic Activities for Oxidative C−C Bond Cleavage of Unsaturated Hydrocarbons
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-201511203754
dc.contributor.laitosKemian laitosfi
dc.contributor.laitosDepartment of Chemistryen
dc.contributor.oppiaineEpäorgaaninen ja analyyttinen kemiafi
dc.contributor.oppiaineInorganic and Analytical Chemistryen
dc.type.urihttp://purl.org/eprint/type/JournalArticle
dc.date.updated2015-11-20T13:15:19Z
dc.type.coarhttp://purl.org/coar/resource_type/c_2df8fbb1
dc.description.reviewstatuspeerReviewed
dc.format.pagerange11062-11070
dc.relation.issn0020-1669
dc.relation.numberinseries23
dc.relation.volume47
dc.type.versionacceptedVersion
dc.rights.copyright© 2008 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.
dc.rights.accesslevelopenAccessfi
dc.subject.ysokatalyysi
jyx.subject.urihttp://www.yso.fi/onto/yso/p8704
dc.relation.doi10.1021/ic801352d
dc.type.okmA1


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