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Tandem Reactivity of Metal−Carbon and Carbon−Silicon Bonds in Mononuclear α-Silyl Organolithium or Organosodium Complexes Towards CO, CO₂ and Heteroallenes

Lookup NU author(s): Dr Jack Hemingway, Dr Paul Waddell, Dr James DawsonORCiD

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This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).

Abstract

© 2026 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.α-Silyl alkyl complexes, such as the ubiquitous MCH2SiMe3, are some of the most used organometallic building blocks and reagents. Hitherto, most reports focus on the reactive metal–carbon bond, while the carbon–silicon bond has thus far been limited to a handful of serendipitous reaction patterns. Herein, by examining a range of reactions between mononuclear Li or Na α-silyl alkyl complexes and CO, CO2, or heteroallenes (isocyanates, isothiocyanates, carbodiimides), we report tandem M─C and C─Si bond reactivity, with in-depth mechanistic understanding unveiled by computational reaction pathway studies enabled by the artificial force induced reaction (AFIR) method. By bringing the long-neglected C─Si bond reactivity to the awareness of synthetic chemists, we demonstrate that the C─Si bond should be taken into account in reaction design when using these α-silyl alkyl complexes.

Publication metadata

Author(s): Yang X, Hemingway JM, Kanna W, Davison N, Hayashi H, Male L, Waddell PG, Dawson JA, Lu E

Publication type: Article

Publication status: Published

Journal: Angewandte Chemie - International Edition

Year: 2026

Volume: 65

Issue: 21

Online publication date: 11/04/2026

Acceptance date: 01/04/2026

Date deposited: 27/04/2026

ISSN (print): 1433-7851

ISSN (electronic): 1521-3773

Publisher: John Wiley and Sons Inc

URL: https://doi.org/10.1002/anie.8906317

DOI: 10.1002/anie.8906317

Data Access Statement: The Supporting Information is available free of charge for additional experimental details, materials, and methods. CCDC 2324926 ( 3 ), 2324927 ( 4 ), 2439663 ( 5 ), 2531967 ( 6 ), 2533795 ( 7 ), 2533796 ( 8 ), 2533797 ( 9 ), 2539212 ( 10 ) and 2533798 ( 11 ) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam. ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: + 44 1223 336033.

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