Shiri, FarshadAriafard, Alireza2025-12-172025-12-171359-7345PubMed:36994794ORCID:/0000-0003-2383-6380/work/198105695https://hdl.handle.net/1885/733795700This study demonstrates that the oxidative addition of hypervalent iodine PhICl2 to Au(i) complexes LAuAr follows an unprecedented stepwise mechanism. The energy of the Au(i) dx2−y2 orbital determines the ease of the oxidative addition reaction; the fewer electron-withdrawing substituents present on the Ar ligand, the higher the energy of the dx2−y2 orbital and the easier the oxidative addition.We thank the Australian Research Council (ARC) for project funding (DP180100904) and the Australian National Computational Infrastructure and University of Tasmania for the generous allocation of computing time.4en© 2023 The Author(s)2023-03-2210.1039/d3cc00543g85151851055