Solvent‐Driven Interconversion of Pyridine Dicarbanion‐Bonded Ag ₁₃ Nanocluster Isomers

Abstract Solvent screening is pivotal for optimizing metal‐catalyzed reactions, yet its impact on the in situ formation and reactivity of polynuclear organometallic clusters remains underexplored. We herein isolate two distinct thirteen‐membered silver cluster isomers, Ag 13 ‐A and Ag 13 ‐M , in acetone and methanol, respectively. Significantly, we demonstrate the interconversion of these isomers facilitated by solvent manipulation. Mechanistic studies on the solvent‐driven Ag 13 ‐A to Ag 13 ‐M transformation reveal this transformation proceeds with a low activation energy (23.39 ± 0.81 kcal mol −1 ) and positive entropy, involving counter anion dissociation, ligand twisting, and re‐coordination. The observed differences in thermal stability and reactivity between two isomers are attributed to variations in Ag–Ag interactions and surface ligand arrangements, underscoring the critical role of solvent selection in affecting the whole organic transformation through in situ formed clusters. These results highlight the necessity of considering organometallic cluster intermediates in solvent screening.