Preparation of α‐ <i>Mono</i> ‐Fluoromethyl Silanes <i>via</i> Nucleophilic Displacement on Chlorosilanes With LiCH ₂ F

Though surprising – when compared with well‐established poly‐ fluoromethyl silanes (e.g., Ruppert‐Prakash reagent, TMSCF 3 ) – α‐ mono ‐fluoromethyl silanes are underrepresented motifs in chemical synthesis, having been – so far – reported no more than 2–3 examples. We propose herein the nucleophilic substitution on the silicon atom of chlorosilanes – with fluoromethyllithium (LiCH 2 F) – as a general strategy for their direct preparation. The procedure ‐ exhibiting remarkable dependance on steric elements across silicon – can be advantageously extended to prepare distinct IV‐row heteroatom‐centered analogues such as tin and germanium organometallics.