Tandem Reactivity of Metal−Carbon and Carbon−Silicon Bonds in Mononuclear α‐Silyl Organolithium or Organosodium Complexes Towards CO, CO ₂ and Heteroallenes

ABSTRACT α‐Silyl alkyl complexes, such as the ubiquitous MCH 2 SiMe 3 , 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, CO 2 , 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.