Show simple item record

Ferrocene-Based N-Heterocyclic Plumbylenes [Fe{(η⁵- C₅H₄)NSiMe₂R}₂Pb:]: Influence of the Steric Demand of the NSubstituents on Their Dimerization via C-H Activation with Pbᴵᴵ

dc.date.accessioned2023-07-24T15:24:07Z
dc.date.available2023-07-24T15:24:07Z
dc.date.issued2023-05-12
dc.identifierdoi:10.17170/kobra-202307248470
dc.identifier.urihttp://hdl.handle.net/123456789/14922
dc.description.sponsorshipGefördert im Rahmen des Projekts DEAL
dc.language.isoeng
dc.rightsNamensnennung 4.0 International*
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/*
dc.subjectcarbene homologueseng
dc.subjectleadeng
dc.subjectmetalloceneseng
dc.subjectsteric hindranceeng
dc.subjectsubvalent compoundseng
dc.subject.ddc540
dc.titleFerrocene-Based N-Heterocyclic Plumbylenes [Fe{(η⁵- C₅H₄)NSiMe₂R}₂Pb:]: Influence of the Steric Demand of the NSubstituents on Their Dimerization via C-H Activation with Pbᴵᴵeng
dc.typeAufsatz
dcterms.abstractFerrocene-based N-heterocyclic plumbylenes fc[(NSiMe₂R)₂Pb:] (1; fc=1,1’-ferrocenylene) are easily accessible by transamination from [(Me₃Si)₂N]₂Pb and the corresponding 1,1’-diaminoferrocene derivatives fc(NHSiMe₂R)₂. They may form unconventional dimers 2 by a process, which causes the cleavage of a cyclopentadienyl C−H bond and the formation of a Pb−C and an N−H bond. The monomer-dimer equilibrium (2 1⇆2) has been addressed experimentally and computationally. It critically depends on the steric demand of the N-substituents SiMe₂R, which has been varied systematically by using homologues with aliphatic (R=methyl, ethyl, isopropyl, tert-butyl) and aromatic units (R=phenyl, mesityl, ferrocenyl). Even in the sterically least congested case (R=methyl), dimerization is only slightly exergonic. It eventually becomes prohibitively endergonic with increasingly larger substituents and is thus not observed for R=tert-butyl, mesityl, and ferrocenyl. R=phenyl represents a borderline case, where the dimer is still detectable in the equilibrium mixture, albeit as a very minor component, in accord with the slightly endergonic Gibbs free energy change calculated for its formation. Addition of 4-dimethylaminopyridine (DMAP) to the monomer-dimer equilibrium mixtures cleanly affords the corresponding adducts [1(DMAP)], irrespective of the equilibrium composition.eng
dcterms.accessRightsopen access
dcterms.creatorGuthardt, Robin
dcterms.creatorJacob, Hannes Lukas
dcterms.creatorHerle, Dominic
dcterms.creatorLeibold, Michael
dcterms.creatorBruhn, Clemens
dcterms.creatorHeinz, Myron
dcterms.creatorHolthausen, Max C.
dcterms.creatorSiemeling, Ulrich
dcterms.extent9 Seiten
dc.relation.doidoi:10.1002/asia.202300266
dc.subject.swdBleiger
dc.subject.swdCarbenkomplexeger
dc.subject.swdMetalloceneger
dc.subject.swdSterische Hinderungger
dc.type.versionpublishedVersion
dcterms.source.identifiereissn:1861-471X
dcterms.source.issueIssue 13
dcterms.source.journalChemistry - An Asian Journaleng
dcterms.source.volumeVolume 18
kup.iskupfalse
dcterms.source.articlenumbere202300266


Files in this item

Thumbnail
Name:
Chemistry_An_Asian_Journal_202 ...
Size:
1.422Mb
Format:
PDF
View/Open
Thumbnail
Name:
license_rdf
Size:
908bytes
Format:
application/rdf+xml
View/Open

This item appears in the following Collection(s)

Show simple item record

Namensnennung 4.0 International
Except where otherwise noted, this item's license is described as Namensnennung 4.0 International