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.accessioned | 2023-07-24T15:24:07Z | |
| dc.date.available | 2023-07-24T15:24:07Z | |
| dc.date.issued | 2023-05-12 | |
| dc.identifier | doi:10.17170/kobra-202307248470 | |
| dc.identifier.uri | http://hdl.handle.net/123456789/14922 | |
| dc.description.sponsorship | Gefördert im Rahmen des Projekts DEAL | |
| dc.language.iso | eng | |
| dc.rights | Namensnennung 4.0 International | * |
| dc.rights.uri | http://creativecommons.org/licenses/by/4.0/ | * |
| dc.subject | carbene homologues | eng |
| dc.subject | lead | eng |
| dc.subject | metallocenes | eng |
| dc.subject | steric hindrance | eng |
| dc.subject | subvalent compounds | eng |
| dc.subject.ddc | 540 | |
| dc.title | 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 | eng |
| dc.type | Aufsatz | |
| dcterms.abstract | Ferrocene-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.accessRights | open access | |
| dcterms.creator | Guthardt, Robin | |
| dcterms.creator | Jacob, Hannes Lukas | |
| dcterms.creator | Herle, Dominic | |
| dcterms.creator | Leibold, Michael | |
| dcterms.creator | Bruhn, Clemens | |
| dcterms.creator | Heinz, Myron | |
| dcterms.creator | Holthausen, Max C. | |
| dcterms.creator | Siemeling, Ulrich | |
| dcterms.extent | 9 Seiten | |
| dc.relation.doi | doi:10.1002/asia.202300266 | |
| dc.subject.swd | Blei | ger |
| dc.subject.swd | Carbenkomplexe | ger |
| dc.subject.swd | Metallocene | ger |
| dc.subject.swd | Sterische Hinderung | ger |
| dc.type.version | publishedVersion | |
| dcterms.source.identifier | eissn:1861-471X | |
| dcterms.source.issue | Issue 13 | |
| dcterms.source.journal | Chemistry - An Asian Journal | eng |
| dcterms.source.volume | Volume 18 | |
| kup.iskup | false | |
| dcterms.source.articlenumber | e202300266 |
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