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dc.contributor.authorHoughton, Adrian
dc.contributor.authorKarttunen, Virve
dc.contributor.authorFan, Cheng
dc.contributor.authorPiers, Warren
dc.contributor.authorTuononen, Heikki
dc.date.accessioned2015-12-01T06:52:33Z
dc.date.available2015-12-01T06:52:33Z
dc.date.issued2013
dc.identifier.citationHoughton, A., Karttunen, V., Fan, C., Piers, W., & Tuononen, H. (2013). Mechanistic Studies on the Metal-Free Activation of Dihydrogen by Antiaromatic Pentarylboroles. <i>Journal of the American Chemical Society</i>, <i>135</i>(2), 941-947. <a href="https://doi.org/10.1021/ja311842r" target="_blank">https://doi.org/10.1021/ja311842r</a>
dc.identifier.otherCONVID_22397472
dc.identifier.otherTUTKAID_56336
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/47892
dc.description.abstractThe perfluoro- and perprotiopentaphenylboroles 1 and 2 react with dihydrogen to effect H–H bond cleavage and formation of boracyclopentene products. The mechanism of this reaction has been studied experimentally through evaluation of the kinetic properties of the slower reaction between 2 and H2. The reaction is first-order in both [borole] and [H2] with activation parameters of ΔH⧧ = 34(8) kJ/mol and ΔS⧧ = −146(25) J mol–1 K–1. A minimal kinetic isotope effect of 1.10(5) was observed, suggesting an asynchronous geometry for H–H cleavage in the rate-limiting transition state. To explain the stereochemistry of the observed products, a ring-opening/ring-closing mechanism is proposed and supported by the separate synthesis of a proposed intermediate and its observed conversion to product. Furthermore, extensive DFT mapping of the reaction mechanism supports the plausibility of this proposal. The study illustrates a new mechanism for the activation of H2 by a strong main group Lewis acid in the absence of an external base, a process driven in part by the antiaromaticity of the borole rings in 1 and 2.
dc.language.isoeng
dc.publisherAmerican Chemical Society
dc.relation.ispartofseriesJournal of the American Chemical Society
dc.subject.othervedyn aktivointi
dc.subject.otherborrolit
dc.subject.otherhydrogen activation
dc.subject.otherboroles
dc.titleMechanistic Studies on the Metal-Free Activation of Dihydrogen by Antiaromatic Pentarylboroles
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-201511243796
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.updated2015-11-24T13:15:23Z
dc.type.coarhttp://purl.org/coar/resource_type/c_2df8fbb1
dc.description.reviewstatuspeerReviewed
dc.format.pagerange941-947
dc.relation.issn0002-7863
dc.relation.numberinseries2
dc.relation.volume135
dc.type.versionacceptedVersion
dc.rights.copyright© 2012 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/ja311842r
dc.type.okmA1


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