Ariafard, AlirezaHyland, Christopher J.T.Canty, Allan J.Sharma, ManabBrookes, Nigel J.Yates, Brian F.2026-01-012026-01-010020-1669ORCID:/0000-0003-2383-6380/work/163628685https://hdl.handle.net/1885/733800838Ligand effects in bimetallic high oxidation state systems containing a X-Pd-Pd-Y framework have been explored with density functional theory (DFT). The ligand X has a strong effect on the dissociation reaction of Y to form [X-Pd-Pd]+ + Y-. In the model system examined where Y is a weak σ-donor ligand and a good leaving group, we find that dissociation of Y is facilitated by greater σ-donor character of X relative to Y. We find that there is a linear correlation of the Pd-Y and Pd-Pd bond lengths with Pd-Y bond dissociation energy, and with the σ-donating ability of X. These results can be explained by the observation that the Pd dz2 population in the PdY fragment increases as the donor ability of X increases. In these systems, the PdIII-PdIII arrangement is favored when X is a weak σ-donor ligand, while the PdIV-PdII arrangement is favored when X is a strong σ-donor ligand. Finally, we demonstrate that ligand exchange to form a bimetallic cationic species in which each Pd is six-coordinate should be feasible in a high polarity solvent.5en2010-12-0610.1021/ic102091278650239417