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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
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202000009
Subject(s) - cycloaddition , silylene , chemistry , reactivity (psychology) , carbene , ethylene , nickel , olefin fiber , medicinal chemistry , yield (engineering) , photochemistry , computational chemistry , organic chemistry , catalysis , materials science , silicon , medicine , alternative medicine , pathology , metallurgy
The versatile cycloaddition chemistry of the Si−Ni multiple bond in the acyclic (amido)(chloro)silylene→Ni 0 complex 1 , [( TMS L)ClSi→Ni(NHC) 2 ] ( TMS L=N(SiMe 3 )Dipp; Dipp=2,6‐ i Pr 2 C 6 H 4 ; NHC=C[( i Pr)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 sp 2 ‐CH bond activation, via a 1‐nickela‐4‐silacyclohexane intermediate. These results have been supported by DFT calculations giving insights into key mechanistic aspects.