Investigation of (Me 4 N)SCF 3 as a Stable, Solid and Safe Reservoir for S=CF 2 as a Surrogate for Thiophosgene

While thiophosgene finds widespread usage on a multi‐ton scale, its fluorinated counterpart S=CF 2 is essentially unexplored in synthesis. Using experimental reactivity tests, ReactIR and computational techniques, we herein showcase that the solid (Me 4 N)SCF 3 functions as a safe reservoir for S=CF 2 . A key feature is that the reactive electrophile is not simply released over time, but instead is liberated under activation with a protic nucleophile. The reactivity of S=CF 2 is mild, allowing large‐scale and late‐stage synthetic applications without special reaction control. The mechanism was fully elucidated, including a rationalization of the role of the Me 4 N cation and the origins of selectivity.