Cycloaddition Chemistry of a Silylene‐Nickel Complex toward Organic π‐Systems: From Reversibility to C−H Activation
| dc.contributor.author | Hadlington, Terrance J. | |
| dc.contributor.author | Kostenko, Arseni | |
| dc.contributor.author | Drieß, Matthias | |
| dc.date.accessioned | 2020-02-26T11:27:04Z | |
| dc.date.available | 2020-02-26T11:27:04Z | |
| dc.date.issued | 2020-01-31 | |
| dc.description.abstract | The versatile cycloaddition chemistry of the Si−Ni multiple bond in the acyclic (amido)(chloro)silylene→Ni0 complex 1, [(TMSL)ClSi→Ni(NHC)2] (TMSL=N(SiMe3)Dipp; Dipp=2,6‐iPr2C6H4; NHC=C[(iPr)NC(Me)]2), toward unsaturated organic substrates is reported, which is both reminiscent of and expanding on the reactivity patterns of classical Fischer and Schrock carbene–metal complexes. Thus, 1:1 reaction of 1 with aldehydes, imines, alkynes, and even alkenes proceed to yield [2+2] cycloaddition products, leading to a range of four‐membered metallasilacycles. This cycloaddition is in fact reversible for ethylene, whereas addition of an excess of this olefin leads to quantitative sp2‐CH bond activation, via a 1‐nickela‐4‐silacyclohexane intermediate. These results have been supported by DFT calculations giving insights into key mechanistic aspects. | en |
| dc.description.sponsorship | DFG, 390540038, EXC 2008: UniSysCat | en |
| dc.description.sponsorship | TU Berlin, Open-Access-Mittel - 2020 | en |
| dc.identifier.eissn | 1521-3765 | |
| dc.identifier.issn | 0947-6539 | |
| dc.identifier.uri | https://depositonce.tu-berlin.de/handle/11303/10839 | |
| dc.identifier.uri | http://dx.doi.org/10.14279/depositonce-9734 | |
| dc.language.iso | en | en |
| dc.rights.uri | https://creativecommons.org/licenses/by/4.0/ | en |
| dc.subject.ddc | 540 Chemie und zugeordnete Wissenschaften | de |
| dc.subject.other | carbene analogues | en |
| dc.subject.other | bond activation | en |
| dc.subject.other | metal complexes | en |
| dc.subject.other | silametallacycles | en |
| dc.subject.other | silicon | en |
| dc.title | Cycloaddition Chemistry of a Silylene‐Nickel Complex toward Organic π‐Systems: From Reversibility to C−H Activation | en |
| dc.type | Article | en |
| dc.type.version | publishedVersion | en |
| dcterms.bibliographicCitation.doi | 10.1002/chem.202000009 | en |
| dcterms.bibliographicCitation.issue | 9 | en |
| dcterms.bibliographicCitation.journaltitle | Chemistry - A European Journal | en |
| dcterms.bibliographicCitation.originalpublishername | Wiley-VCH | en |
| dcterms.bibliographicCitation.originalpublisherplace | Weinheim | en |
| dcterms.bibliographicCitation.pageend | 1962 | en |
| dcterms.bibliographicCitation.pagestart | 1958 | en |
| dcterms.bibliographicCitation.volume | 26 | en |
| tub.accessrights.dnb | free | en |
| tub.affiliation | Fak. 2 Mathematik und Naturwissenschaften::Inst. Chemie::FG Metallorganische Chemie und Anorganische Materialien | de |
| tub.affiliation.faculty | Fak. 2 Mathematik und Naturwissenschaften | de |
| tub.affiliation.group | FG Metallorganische Chemie und Anorganische Materialien | de |
| tub.affiliation.institute | Inst. Chemie | de |
| tub.publisher.universityorinstitution | Technische Universität Berlin | en |