In conclusion, we have developed a general and mild thioetherification between thiols and halogenated heterocycles. Control experiments, 1 H NMR titration, RPKA, and computational studies support a unique mechanism involving dual nucleophile and electrophile ionization through a RLPT event, followed by cSNAr. We synthesized >70 products derived from thiols and halogenated heterocycles sampling a significant range of functionality often encountered in pharmaceutical discovery. By merging HTE with data science tools, we have developed an interpretive and predictive classification model for product formation that was validated using known complex targets. The model's interpretability facilitates the analysis of heuristics relevant to this reaction type. We believe that combining these heuristics with the accurate and efficient predictions of the classification model will save valuable time and experimentation when preparing thioethers for diverse applications ranging medicinal chemistry library generation to commercial manufacture. Finally, PTDI SNAr compliments modern synthetic approaches to thioethers and motivates additional research evaluating PTDI as a general activation mode between nucleophiles and electrophiles.