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dc.contributor.authorLe Coz, Erwann
dc.contributor.authorZhang, Ziyun
dc.contributor.authorRoisnel, Thierry
dc.contributor.authorCavallo, Luigi
dc.contributor.authorFalivene, Laura
dc.contributor.authorCarpentier, Jean-François
dc.contributor.authorSarazin, Yann
dc.date.accessioned2019-12-08T10:45:16Z
dc.date.available2019-12-08T10:45:16Z
dc.date.issued2020-02-25
dc.date.submitted2019-10-29
dc.identifier.citationLe Coz, E., Zhang, Z., Roisnel, T., Cavallo, L., Falivene, L., Carpentier, J., & Sarazin, Y. (2020). Barium-Catalysed Dehydrocoupling of Hydrosilanes and Borinic Acids: A Mechanistic Insight. Chemistry – A European Journal. doi:10.1002/chem.201904933
dc.identifier.doi10.1002/chem.201904933
dc.identifier.doi10.1002/chem.202000478
dc.identifier.doi10.1002/chem.202000477
dc.identifier.urihttp://hdl.handle.net/10754/660449
dc.description.abstractTwo very rare cases of barium boryloxides, the homoleptic [Ba(OB{CH(SiMe3)2}2)2⋅C7H8] and the heteroleptic [{LONO4}BaOB{CH(SiMe3)2}2] stabilised by the multidentate aminoetherphenolate {LONO4}−, are presented, and their structural properties are discussed. The electron-deficient [Ba(OB{CH(SiMe3)2}2)2⋅C7H8] shows, in particular, resilient η6-coordination of the toluene molecule. Together with its amido parents [Ba{N(SiMe3)2}2⋅thf2] and [Ba{N(SiMe3)2}2]2, this complex catalyses the fast and chemoselective dehydrocoupling of borinic acids R2BOH and hydrosilanes HSiR′3, yielding borasiloxanes R2BOSiR′3 in a controlled fashion. The assessment of substrate scope indicates that, for now, the reaction is limited to bulky borinic acids. Kinetic analysis shows that the rate-limiting step of the catalytic manifold traverses a dinuclear transition state. A detailed mechanistic scenario is proposed on the basis of DFT computations, the results of which are fully consistent with experimental data. It consists of a stepwise process with rate-determining nucleophilic attack of a metal-bound O-atom onto the incoming hydrosilane, involving throughout dinuclear catalytically active species.
dc.description.sponsorshipL.C., L.F. and Z.Z. thank the King Abdullah University of Science and Technology (KAUST) for supporting this work. For computer time, this research used the resources of the KAUST Super-computing Laboratory (KSL) at KAUST. E.L.C. thanks the Univer-sity of Rennes 1 for a PhD grant.
dc.publisherWiley
dc.relation.urlhttps://onlinelibrary.wiley.com/doi/abs/10.1002/chem.202000478
dc.rightsArchived with thanks to Chemistry (Weinheim an der Bergstrasse, Germany)
dc.titleBarium-Catalysed Dehydrocoupling of Hydrosilanes and Borinic Acids: A Mechanistic Insight.
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalChemistry (Weinheim an der Bergstrasse, Germany)
dc.rights.embargodate2021-02-26
dc.eprint.versionPost-print
dc.contributor.institutionCNRS, ISCR (Institut des Sciences Chimiques de Rennes)-UMR 6226, Univ Rennes, 35000, Rennes, France.
kaust.personZhang, Ziyun
kaust.personCavallo, Luigi
kaust.personFalivene, Laura
dc.date.accepted2019-11-22
dc.relation.issupplementedbyDOI:10.5517/ccdc.csd.cc23vcfs
dc.relation.issupplementedbyDOI:10.5517/ccdc.csd.cc23vcdr
refterms.dateFOA2019-12-08T10:46:50Z
display.relations<b>Is Supplemented By:</b><br/> <ul><li><i>[Dataset]</i> <br/> Le Coz, Erwann, Zhang, Ziyun, Roisnel, Thierry, Cavallo, Luigi, Falivene, Laura, Carpentier, Jean-François, &amp; Sarazin, Yann. (2020). <i>CCDC 1961755: Experimental Crystal Structure Determination</i> [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/CCDC.CSD.CC23VCFS. DOI: <a href="https://doi.org/10.5517/ccdc.csd.cc23vcfs" >10.5517/ccdc.csd.cc23vcfs</a> Handle: <a href="http://hdl.handle.net/10754/669189" >10754/669189</a></a></li><li><i>[Dataset]</i> <br/> Le Coz, Erwann, Zhang, Ziyun, Roisnel, Thierry, Cavallo, Luigi, Falivene, Laura, Carpentier, Jean-François, &amp; Sarazin, Yann. (2020). <i>CCDC 1961754: Experimental Crystal Structure Determination</i> [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/CCDC.CSD.CC23VCDR. DOI: <a href="https://doi.org/10.5517/ccdc.csd.cc23vcdr" >10.5517/ccdc.csd.cc23vcdr</a> Handle: <a href="http://hdl.handle.net/10754/669190" >10754/669190</a></a></li></ul>
dc.date.published-online2020-02-25
dc.date.published-print2020-03-18


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