PhICl₂ is a widely employed hypervalent iodine reagent, valued for its role as a chlorinating agent and oxidant in organic synthesis. While experimental studies have suggested that amines or chlorides can activate the complex, the exact mechanistic pathway remains unclear. Herein, we report an exploration of routes for dissociation involving molecular chlorine generation. To this end, we employ transition state search techniques, including NEB and QST2, alongside standard geometry optimizations and vibrational frequency analyses to elucidate potential pathways. Additionally, we benchmark various DFT methods against crystal structure data for various bis-ligated aryl-λ³-iodane (ArIL₂) complexes to ensure accurate computational modeling of reaction energetics.