Metal nitrene-like reactivity of a SiN bond towards CO2

Terrance J. Hadlington; Tibor Szilvási; Matthias Driess

doi:10.1039/C8CC05238G

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Metal nitrene-like reactivity of a SiN bond towards CO₂†

Terrance J. Hadlington,

^a Tibor Szilvási^b and Matthias Driess

*^a

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* Corresponding authors

^a Department of Chemistry, Metalorganics and Inorganic Materials, Techniche Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623 Berlin, Germany
E-mail: matthias.driess@tu-berlin.de

^b Department of Chemical & Biological Engineering, University of Wisconsin—Madison, 1415 Engineering Drive, Madison, WI, USA

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 SiN bonds is formed exclusively.

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Article information

DOI: https://doi.org/10.1039/C8CC05238G
Article type: Communication
Submitted: 29 Jun 2018
Accepted: 30 Jul 2018
First published: 30 Jul 2018

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Chem. Commun., 2018,54, 9352-9355

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Metal nitrene-like reactivity of a SiN bond towards CO₂

T. J. Hadlington, T. Szilvási and M. Driess, Chem. Commun., 2018, 54, 9352 DOI: 10.1039/C8CC05238G

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