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Silylated silicon–carbonyl complexes as mimics of ubiquitous transition-metal carbonyls

Nature Chemistry volume 12, pages 1131–1135 (2020)Cite this article

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Abstract

Transition-metal–carbonyl complexes are common organometallic reagents that feature metal–CO bonds. These complexes have proven to be powerful catalysts for various applications. By contrast, silicon–carbonyl complexes, organosilicon reagents poised to be eco-friendly alternatives for transition-metal carbonyls, have remained largely elusive. They have mostly been explored theoretically and/or through low-temperature matrix isolation studies, but their instability had typically precluded isolation under ambient conditions. Here we present the synthesis, isolation and full characterization of stable silyl-substituted silicon–carbonyl complexes, along with bonding analysis. Initial reactivity investigations showed examples of CO liberation, which could be induced either thermally or photochemically, as well as substitution and functionalization of the CO moiety. Importantly, the complexes exhibit strong Si–CO bonding, with CO→Si σ-donation and Si→CO π-backbonding, which is reminiscent of transition-metal carbonyls. This similarity between the abundant semi-metal silicon and rare transition metals may provide new opportunities for the development of silicon-based catalysis.

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Fig. 1: Selected examples of isolable main group carbonyl complexes.
Fig. 2: Synthesis and transition-metal mimic chemistry of silicon–carbonyl complex [(TMS)3Si](tBu3Si)Si⇆CO (3) (TMS = trimethylsilyl).
Fig. 3: Molecular structures of compounds 3 and 5 with thermal ellipsoids set at 50% probability as derived from SC-XRD analysis.
Fig. 4: Bonding analysis of [(TMS)3Si](tBu3Si)SiCO (3).
Fig. 5: Reactivity of carbonyl complexes with azides.

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Data availability

X-ray crystallographic data are available free of charge from the Cambridge Crystallographic Data Centre under the reference numbers CCDC 1976834 (3) and CCDC 1976835 (5) via https://www.ccdc.cam.ac.uk/structures/. All other data supporting the findings are contained in the main text or the Supplementary Information.

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Acknowledgements

We thank M. C. Holthausen and J. I. Schweizer for fruitful discussions, computational resources and advice. Quantum chemical calculations were performed in part at the Leibniz Supercomputing Center of the Bavarian Academy of Science and Humanities. We acknowledge M. Muhr (R. A. Fischer) for the LIFDI-MS measurement. We thank the WACKER Chemie AG and the European Research Council (SILION 637394) for continued financial support.

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Authors and Affiliations

  1. Department of Chemistry, WACKER-Institute of Silicon Chemistry and Catalysis Research Center, Technische Universität München, Garching bei München, Germany

    Dominik Reiter, Richard Holzner, Amelie Porzelt, Philipp Frisch & Shigeyoshi Inoue

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Contributions

D.R. and R.H. planned and carried out all experiments and analysed the data. A.P. designed and conducted the computational investigations. P.F. performed the SC-XRD measurements. S.I. designed and conceived the project. D.R. and S.I. wrote the manuscript with input and critical revision from all authors.

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Correspondence to Shigeyoshi Inoue.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–39, Discussion and Tables 1–27.

Supplementary Data 1

Cif file compound 3.

Supplementary Data 2

Cif file compound 5.

Supplementary Data

Cartesian coordinates for the optimized structures.

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Reiter, D., Holzner, R., Porzelt, A. et al. Silylated silicon–carbonyl complexes as mimics of ubiquitous transition-metal carbonyls. Nat. Chem. 12, 1131–1135 (2020). https://doi.org/10.1038/s41557-020-00555-4

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