Peripheral mechanism of a carbonyl hydrosilylation catalysed by an SiNSi iron pincer complex

dc.contributor.authorMetsänen, Toni Tapio
dc.contributor.authorGallego, Daniel
dc.contributor.authorSzilvasi, Tibor
dc.contributor.authorDrieß, Matthias
dc.contributor.authorOestreich, Martin
dc.date.accessioned2017-10-25T06:24:43Z
dc.date.available2017-10-25T06:24:43Z
dc.date.issued2015
dc.description.abstractCombined experimental and theoretical analysis of the carbonyl hydrosilylation catalysed by an iron(0) pincer complex reveals an unprecedented mechanism of action. The iron(0) complex is in fact a precatalyst that is converted into an iron(II) catalyst through oxidative addition of a hydrosilane. Neither the hydrogen atom nor the silicon atom bound to the iron(II) centre are subsequently transferred onto the carbonyl acceptor, instead remaining at the sterically inaccessible iron(II) atom throughout the catalytic cycle. A series of labelling, crossover and competition experiments as well as the use of a silicon-stereogenic hydrosilane as a stereochemical probe suggest that the iron(II) site is not directly involved in the hydrosilylation. Strikingly, it is the silyl ligand attached to the iron(II) atom that acts as a Lewis acid for carbonyl activation in this catalysis. The whole catalytic process occurs on the periphery of the transition metal. Computation of the new peripheral as well as plausible alternative inner and outer sphere mechanisms support the experimental findings.en
dc.description.sponsorshipDFG, EXC 314, Unifying Concepts in Catalysisen
dc.identifier.eissn2041-6539
dc.identifier.issn2041-6520
dc.identifier.urihttps://depositonce.tu-berlin.de//handle/11303/6931
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-6270
dc.language.isoen
dc.rights.urihttps://creativecommons.org/licenses/by/3.0/
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.titlePeripheral mechanism of a carbonyl hydrosilylation catalysed by an SiNSi iron pincer complexen
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1039/c5sc02855h
dcterms.bibliographicCitation.issue12
dcterms.bibliographicCitation.journaltitleChemical Scienceen
dcterms.bibliographicCitation.originalpublishernameRoyal Society of Chemistryde
dcterms.bibliographicCitation.originalpublisherplaceCambridgede
dcterms.bibliographicCitation.pageend7149
dcterms.bibliographicCitation.pagestart7143
dcterms.bibliographicCitation.volume6
tub.accessrights.dnbfree
tub.affiliationFak. 2 Mathematik und Naturwissenschaften>Inst. Chemie>FG Organische Chemie / Synthese und Katalysede
tub.affiliationFak. 2 Mathematik und Naturwissenschaften>Inst. Chemie>FG Metallorganische Chemie und Anorganische Materialiende
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.groupFG Organische Chemie / Synthese und Katalysede
tub.affiliation.groupFG Metallorganische Chemie und Anorganische Materialiende
tub.affiliation.instituteInst. Chemiede
tub.affiliation.instituteInst. Chemiede
tub.publisher.universityorinstitutionTechnische Universität Berlin
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