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Main Title: Cycloaddition Chemistry of a Silylene‐Nickel Complex toward Organic π‐Systems: From Reversibility to C−H Activation
Author(s): Hadlington, Terrance J.
Kostenko, Arseni
Drieß, Matthias
Type: Article
Language Code: en
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.
Issue Date: 31-Jan-2020
Date Available: 26-Feb-2020
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Subject(s): carbene analogues
bond activation
metal complexes
Sponsor/Funder: DFG, 390540038, EXC 2008: UniSysCat
TU Berlin, Open-Access-Mittel - 2020
Journal Title: Chemistry - A European Journal
Publisher: Wiley-VCH
Publisher Place: Weinheim
Volume: 26
Issue: 9
Publisher DOI: 10.1002/chem.202000009
Page Start: 1958
Page End: 1962
EISSN: 1521-3765
ISSN: 0947-6539
Appears in Collections:FG Metallorganische Chemie und Anorganische Materialien » Publications

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