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Equilibrium between a cyclotrisilene and an isolable base adduct of a disilenyl silylene

Abstract

In organic chemistry, compounds with adjacent alkene and carbene functionalities (vinyl carbenes) are studied widely as fleeting intermediates and in the coordination sphere of transition metals. Stable derivatives of vinyl carbenes remain elusive, including the corresponding heavier group 14 homologues. Here we report the isolation and full characterization of a base-stabilized silicon version of a vinyl carbene that features a silicon–silicon double bond as well as a silylene functionality, coordinated by an N-heterocyclic carbene (NHC). In solution, the intensely green disilenyl silylene adduct exists in equilibrium with the corresponding silicon analogue of a cyclopropene and free NHC, which was quantified by nuclear magnetic resonance spectroscopy and ultraviolet–visible spectroscopy. The reversibility of this process raises exciting possibilities for the preparation of extended conjugated π systems of silicon.

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Figure 1: Selected examples of low-valent silicon species stabilized by N-heterocyclic carbenes as reported in the literature.
Figure 2: Equilibrium of cyclotrisilene 1 and N-heterocyclic carbene 2 with NHC-coordinated disilenyl silylene 3 and proposed cyclic intermediate 4.
Figure 3: Molecular structure of 3·C6H12 in the solid state. Hydrogen atoms and co-crystallized cyclohexane are omitted for clarity (thermal ellipsoids at 50%).
Figure 4: UV-vis spectra of 1 (red line) in hexane with increasing concentrations of NHC 2 (other lines).
Figure 5: Frontier molecular orbitals of NHC-coordinated disilenyl silylene 3 at 0.04 atomic units.

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Acknowledgements

We thank the Engineering and Physical Sciences Research Council (EP/H048804/1), the Alfried Krupp Foundation, the European Commission for a Marie-Curie Fellowship (M.J.C.) and P. Jutzi and K. Leszczyńska (Bielefeld) for discussions and suggestions.

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M.J.C. conceived and performed experiments, and co-wrote the manuscript. V.H. determined the solid-state structure of 3. H.S.R. performed the theoretical calculations, co-wrote the manuscript and designed the theoretical part of the study. D.S. designed and coordinated the study and co-wrote the manuscript.

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Correspondence to Henry S. Rzepa or David Scheschkewitz.

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The authors declare no competing financial interests.

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Crystallographic data for compound 3 (CIF 49 kb)

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Cowley, M., Huch, V., Rzepa, H. et al. Equilibrium between a cyclotrisilene and an isolable base adduct of a disilenyl silylene. Nature Chem 5, 876–879 (2013). https://doi.org/10.1038/nchem.1751

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