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Updated: May 10, 2025

Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
Solvent-Driven Interconversion of Pyridine Dicarbanion-Bonded Ag13 Nanocluster Isomers
Cong Jin1, Cui-Cui Li2, Kui Xiao1
1Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing, 100084, China.
None:
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, Ag13-A and Ag13-M, in acetone and methanol, respectively. Significantly, we demonstrate the interconversion of these isomers facilitated by solvent manipulation. Mechanistic studies on the solvent-driven Ag13-A to Ag13-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.
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