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dc.contributor.authorKonu, Jari
dc.contributor.authorTuononen, Heikki
dc.contributor.authorChivers, Tristram
dc.contributor.authorCorrente, Andrea
dc.contributor.authorBoeré, René
dc.contributor.authorRoemmele, Tracey
dc.date.accessioned2015-11-20T09:43:17Z
dc.date.available2015-11-20T09:43:17Z
dc.date.issued2008
dc.identifier.citationKonu, J., Tuononen, H., Chivers, T., Corrente, A., Boeré, R., & Roemmele, T. (2008). In Search of the [PhB(μ-NtBu)2]2As• Radical: Experimental and Computational Investigations of the Redox Chemistry of Group 15 Bis-boraamidinates. <i>Inorganic Chemistry</i>, <i>47</i>(9), 3823-3831. <a href="https://doi.org/10.1021/ic702435e" target="_blank">https://doi.org/10.1021/ic702435e</a>
dc.identifier.otherCONVID_18407512
dc.identifier.otherTUTKAID_33804
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/47768
dc.description.abstractDFT calculations for the group 15 radicals [PhB(μ-NtBu)2]2M• (M = P, As, Sb, Bi) predict a pnictogen-centered SOMO with smaller contributions to the unpaired spin density arising from the nitrogen and boron atoms. The reactions of Li2[PhB(μ-NR)2] (R = tBu, Dipp) with PCl3 afforded the unsolvated complex LiP[PhB(μ-NtBu)2]2 (1a) in low yield and ClP[PhB(μ-NDipp)2] (2), both of which were structurally characterized. Efforts to produce the arsenic-centered neutral radical, [PhB(μ-NtBu)2]2As•, via oxidation of LiAs[PhB(μ-NtBu)2]2 with one-half equivalent of SO2Cl2, yielded the Zwitterionic compound [PhB(μ-NtBu)2As(μ-NtBu)2B(Cl)Ph] (3) containing one four-coordinate boron center with a B−Cl bond. The reaction of 3 with GaCl3 produced the ion-separated salt, [PhB(μ-NtBu)2]2As+GaCl4− (4), which was characterized by X-ray crystallography. The reduction of 3 with sodium naphthalenide occurred by a two-electron process to give the corresponding anion [{PhB(μ-NtBu)2}2As]− as the sodium salt. Voltammetric investigations of 4 and LiAs[PhB(μ-NtBu)2]2 (1b) revealed irreversible processes. Attempts to generate the neutral radical [PhB(μ-NtBu)2]2As• from these ionic complexes via in situ electrolysis did not produce an EPR-active species.
dc.language.isoeng
dc.publisherACS
dc.relation.ispartofseriesInorganic Chemistry
dc.subject.otherboraamidinaatit
dc.subject.otherradikaalit
dc.subject.otherDFT
dc.subject.otherboraamidinates
dc.subject.otherradicals
dc.titleIn Search of the [PhB(μ-NtBu)2]2As• Radical: Experimental and Computational Investigations of the Redox Chemistry of Group 15 Bis-boraamidinates
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-201511193722
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.updated2015-11-19T10:15:12Z
dc.type.coarjournal article
dc.description.reviewstatuspeerReviewed
dc.format.pagerange3823-3831
dc.relation.issn0020-1669
dc.relation.numberinseries9
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/ic702435e


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