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Synthesis, isolation and application of a sila-ketenyl anion

Nature Synthesis volume 2, pages 688–694 (2023)Cite this article

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Abstract

Ynolates or ketenyl anions, [RCCO]−, are negatively charged reactive intermediates, which can be generated in situ and used for divergent chemical transformations. Ynolates can react either at the oxygen or carbon centres or across the C–C triple bond, making them useful in various applications in organic synthesis. Heavier analogues of ynolates or ketenyl anions ([RECO]−, E = group 14 element), however, have not been isolated or studied. Here we report the synthesis, isolation and characterization of [K(18-crown-6)]+[(tBu3Si)SiCO]−, a silicon analogue of a ketenyl anion. [K(18-crown-6)]+[(tBu3Si)SiCO]− is readily prepared through reaction of [K(18-crown-6)]+ coordinated silyl-radical anions with carbon monoxide, or by a reduction of a silyl-substituted silicon–carbonyl complex, [{(Me3Si)3Si}(tBu3Si)SiCO]. X-ray crystallographic and spectroscopic analyses coupled with quantum chemical calculations reveal that [K(18-crown-6)]+[(tBu3Si)SiCO]− predominately displays sila-ketenyl anion character. [(tBu3Si)SiCO]− was also demonstrated to be a competent ligand for a transition metal through reaction with Mo(CO)6.

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Fig. 1: Ynolates and sila-ynolates.
Fig. 2: Synthesis of a sila-ketenyl anion complex [K(18c6)][1].
Fig. 3: X-ray crystal structure of [K(18c6)][1].
Fig. 4: Bonding analysis of sila-ketenyl anion [1]−.
Fig. 5: Synthesis of sila-ketenyl–molybdenum complex [K(18c6)][5].

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Data availability

The data that support the findings of this study are available within the main text and its Supplementary Information. Crystallographic data for compounds [K(18c6)][1], 2, [K(18c6)][2′] and [K(18c6)][5] are available free of charge from the Cambridge Crystallographic Data Centre under references CCDC-2192074, CCDC-2192075, CCDC-2192076 and CCDC-2192077.

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Acknowledgements

This project has received funding from the Alexander von Humboldt foundation for a Research Fellowship (to S.F.) and the European Research Council (ALLOWE 101001591) (to S.I.). We acknowledge M.M.D. Roy for proofreading. We acknowledge M. Ludwig for collection of UV-Vis spectral data. We gratefully acknowledge the Leibniz Supercomputing Centre for funding this project by providing computing time on its Linux-Cluster.

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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

    Shiori Fujimori, Arseni Kostenko & Shigeyoshi Inoue

  2. Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland

    Rosario Scopelliti

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Contributions

S.F. conceived and performed the synthetic experiments and analysed the data. A.K. designed and performed the theoretical analyses. S.F. and R.S. solved and revised the XRD data. S.I. conceived and supervised the project. S.F., A.K. and S.I. wrote the manuscript.

Corresponding author

Correspondence to Shigeyoshi Inoue.

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Nature Synthesis thanks D. Scheschkewitz and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: T. West, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary Figs. 1−35, Tables 1−8, Scheme 1 and Discussion.

Supplementary Data 1

Crystallographic data for [K(18c6)][1] CCDC-2192074.

Supplementary Data 2

Crystallographic data for 2 CCDC-2192075.

Supplementary Data 3

Crystallographic data for [K(18c6)][2′] CCDC-2192076.

Supplementary Data 4

Crystallographic data for [K(18c6)][5] CCDC-2192077.

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Fujimori, S., Kostenko, A., Scopelliti, R. et al. Synthesis, isolation and application of a sila-ketenyl anion. Nat. Synth 2, 688–694 (2023). https://doi.org/10.1038/s44160-023-00283-w

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