Cycloaddition Chemistry of a Silylene-Nickel Complex toward Organic π-Systems: From Reversibility to C-H Activation.
Chemistry
; 26(9): 1958-1962, 2020 Feb 11.
Article
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| MEDLINE
| ID: mdl-31898825
ABSTRACT
The versatile cycloaddition chemistry of the Si-Ni multiple bond in the acyclic (amido)(chloro)silyleneâNi0 complexâ
1, [(TMS L)ClSiâNi(NHC)2 ] (TMS L=N(SiMe3 )Dipp; Dipp=2,6-iPr2 C6 H4 ; 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, 11 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.
Texto completo:
1
Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
Chemistry
Asunto de la revista:
QUIMICA
Año:
2020
Tipo del documento:
Article
País de afiliación:
Alemania