Trifluoromethylthiolation of Aryl Iodides and Bromides Enabled by a Bench‐Stable and Easy‐To‐Recover Dinuclear Palladium(I) Catalyst

While palladium catalysis is ubiquitous in modern chemical research, the recovery of the active transition‐metal complex under routine laboratory applications is frequently challenging. Described herein is the concept of alternative cross‐coupling cycles with a more robust (air‐, moisture‐, and thermally‐stable) dinuclear Pd^I complex, thus avoiding the handling of sensitive Pd⁰ species or ligands. Highly efficient C? SCF₃ coupling of a range of aryl iodides and bromides was achieved, and the recovery of the Pd^I complex was accomplished via simple open‐atmosphere column chromatography. Kinetic and computational data support the feasibility of dinuclear Pd^I catalysis. A novel SCF₃‐bridged Pd^I dimer was isolated, characterized by X‐ray crystallography, and verified to be a competent catalytic intermediate.