Metal nitrene-like reactivity of a Si[double bond, length as m-dash]N bond towards CO2
Terrance J Hadlington1, Tibor Szilvási, Matthias Driess
1Department of Chemistry, Metalorganics and Inorganic Materials, Techniche Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin, Germany. matthias.driess@tu-berlin.de.
Abstract:
The unusual reactivity of the Si[double bond, length as m-dash]N bond in metallo-iminosilane [DippN = Si(OSiMe3)Ni(Cl)(NHC)2] 1 towards CO2 and cyclohexyl isocyanate (CyNCO) is reported; it reacts with two molar equiv. of CO2 to give the [2+2+2] cycloaddition product 3 with complete scission of the σ- and π-Si-N bonds akin to transition-metal nitrene complexes. Theoretical calculations indicate that this reaction is made viable by the high polarity of the Si-N interaction in the intermediary [2+2] cycloaddition product 2, which could also be crystallographically characterised. In the case of isocyanate, the [2+2] cycloaddition product of the C[double bond, length as m-dash]O and Si[double bond, length as m-dash]N bonds is formed exclusively.
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