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dc.contributor.authorDo, Dinh Cao Huan
dc.contributor.authorVasko, Petra
dc.contributor.authorFuentes, M. Ángeles
dc.contributor.authorHicks, Jamie
dc.contributor.authorAldridge, Simon
dc.date.accessioned2020-06-24T08:59:16Z
dc.date.available2020-06-24T08:59:16Z
dc.date.issued2020
dc.identifier.citationDo, D. C. H., Vasko, P., Fuentes, M. Á., Hicks, J., & Aldridge, S. (2020). Probing the non-innocent nature of an amino-functionalised β-diketiminate ligand in silylene/iminosilane systems. <i>Dalton Transactions</i>, <i>49</i>(25), 8701-8709. <a href="https://doi.org/10.1039/D0DT01447H" target="_blank">https://doi.org/10.1039/D0DT01447H</a>
dc.identifier.otherCONVID_36018917
dc.identifier.urihttps://jyx.jyu.fi/handle/123456789/70405
dc.description.abstractElectron-rich β-diketiminate ligands{,} featuring amino groups at the backbone β positions (“N-nacnac” ligands) have been employed in the synthesis of a range of silylene (SiII) complexes of the type (N-nacnac)SiX (where X = H{,} Cl{,} N(SiMe3)2{,} P(SiMe3)2 and Si(SiMe3)3). A combination of experimental and quantum chemical approaches reveals (i) that in all cases rearrangement to give an aza-butadienyl SiIV imide featuring a contracted five-membered heterocycle is thermodynamically favourable (and experimentally viable); (ii) that the kinetic lability of systems of the type (N-nacnac)SiX varies markedly as a function of X{,} such that compounds of this type can be isolated under ambient conditions for X = Cl and P(SiMe3)2{,} but not for X = H{,} N(SiMe3)2 and Si(SiMe3)3; and (iii) that the ring contraction process is most facile for systems bearing strongly electron-donating and sterically less encumbered X groups{,} since these allow most ready access to a transition state accessed via intramolecular nucleophilic attack by the SiII centre at the β-carbon position of the N-nacnac ligand backbone.en
dc.format.mimetypeapplication/pdf
dc.languageeng
dc.language.isoeng
dc.publisherRoyal Society of Chemistry
dc.relation.ispartofseriesDalton Transactions
dc.rightsIn Copyright
dc.titleProbing the non-innocent nature of an amino-functionalised β-diketiminate ligand in silylene/iminosilane systems
dc.typearticle
dc.identifier.urnURN:NBN:fi:jyu-202006244597
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.type.coarhttp://purl.org/coar/resource_type/c_2df8fbb1
dc.description.reviewstatuspeerReviewed
dc.format.pagerange8701-8709
dc.relation.issn1477-9226
dc.relation.numberinseries25
dc.relation.volume49
dc.type.versionacceptedVersion
dc.rights.copyright© 2020 Royal Society of Chemistry
dc.rights.accesslevelopenAccessfi
dc.relation.grantnumber314794
dc.format.contentfulltext
dc.rights.urlhttp://rightsstatements.org/page/InC/1.0/?language=en
dc.relation.doi10.1039/D0DT01447H
dc.relation.funderResearch Council of Finlanden
dc.relation.funderSuomen Akatemiafi
jyx.fundingprogramPostdoctoral Researcher, AoFen
jyx.fundingprogramTutkijatohtori, SAfi
jyx.fundinginformationWe thank Jardine-Oxford Scholarship (DDCH), the Academy of Finland (PV, grant number 314794), the Leverhulme Trust (JH, RP-2018-246) and the EPSRC (MÁF, EP/K014714/1) We also thank the Oxford Advanced Research (ARC) facilities for computing resources
dc.type.okmA1


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