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dc.contributor.authorRobertson, Stuart
dc.contributor.authorChivers, Tristram
dc.contributor.authorTuononen, Heikki
dc.date.accessioned2015-11-25T12:43:52Z
dc.date.available2015-11-25T12:43:52Z
dc.date.issued2008
dc.identifier.citationRobertson, S., Chivers, T., & Tuononen, H. (2008). Experimental and Theoretical Investigations of the Redox Behavior of the Heterodichalcogenido Ligands [(EPiPr2)(TePiPr2)N]− (E = S, Se): Cyclic Cations and Acyclic Dichalcogenide Dimers. <i>Inorganic Chemistry</i>, <i>47</i>(22), 10634-10643. <a href="https://doi.org/10.1021/ic801384c" target="_blank">https://doi.org/10.1021/ic801384c</a>
dc.identifier.otherCONVID_18408048
dc.identifier.otherTUTKAID_33808
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/47834
dc.description.abstractThe two-electron oxidation of the lithium salts of the heterodichalcogenidoimidodiphosphinate anions [(EPiPr2)(TePiPr2)N]− (1a, E = S; 1b, E = Se) with iodine yields cyclic cations [(EPiPr2)(TePiPr2)N]+ as their iodide salts [(SPiPr2)(TePiPr2)N]I (2a) and [(SePiPr2)(TePiPr2)N]I (2b). The five-membered rings in 2a and 2b both display an elongated E−Te bond as a consequence of an interaction between tellurium and the iodide anion. One-electron reduction of 2a and 2b with cobaltocene produces the neutral dimers (EPiPr2NPiPr2Te−)2 (3a, E = S; 3b, E = Se), which are connected exclusively through a Te−Te bond. Two-electron reduction of 2a and 2b with 2 equiv of cobaltocene regenerates the corresponding dichalcogenidoimidodiphosphinate anions as ion-separated cobaltocenium salts Cp2Co[(EPiPr2)(TePiPr2)N] (4a, E = S; 4b, E = Se). The ditellurido analogue Cp2Co[(TePiPr2)2N] (4c) has been prepared in the same manner for comparison. Density functional theory calculations reveal that the preferential interaction of the iodide anion with tellurium is determined by the polarization of the lowest unoccupied molecular orbital [σ*(E−Te)] of the cations in 2a and 2b toward tellurium and that the formation of the dimers 3a and 3b with a central Te−Te linkage is energetically more favorable than the structural isomers with either E−Te or E−E bonds. Compounds 2a, 2b, 3a, 3b, 4a, 4b, and 4c have been characterized in solution by multinuclear NMR spectroscopy and in the solid state by X-ray crystallography.
dc.language.isoeng
dc.publisherACS
dc.relation.ispartofseriesInorganic Chemistry
dc.subject.otherdikalkogenidoligandit
dc.subject.otherhapetus-pelkistys-reaktiot
dc.subject.otherdichalcogenido ligands
dc.subject.otherredox reactions
dc.titleExperimental and Theoretical Investigations of the Redox Behavior of the Heterodichalcogenido Ligands [(EPiPr2)(TePiPr2)N]− (E = S, Se): Cyclic Cations and Acyclic Dichalcogenide Dimers
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-201511203747
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.updated2015-11-20T10:15:33Z
dc.type.coarhttp://purl.org/coar/resource_type/c_2df8fbb1
dc.description.reviewstatuspeerReviewed
dc.format.pagerange10634-10643
dc.relation.issn0020-1669
dc.relation.numberinseries22
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.relation.doi10.1021/ic801384c
dc.type.okmA1


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