Related Experiment Video
Updated: Apr 26, 2026

Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Thermodynamics of the Cu(II) μ-thiolate and Cu(I) disulfide equilibrium: a combined experimental and theoretical
Erica C M Ording-Wenker1, Martijn van der Plas, Maxime A Siegler
1Leiden Institute of Chemistry, Gorlaeus Laboratories, Leiden University , P.O. Box 9502, 2300 RA Leiden, The Netherlands.
Abstract:
The redox equilibrium between dinuclear Cu(II) μ-thiolate and Cu(I) disulfide structures has been analyzed experimentally and via DFT calculations. Two new ligands, L(2)SSL(2) and L(4)SSL(4), and their Cu(II) μ-thiolate and Cu(I) disulfide complexes were synthesized. For L(2)SSL(2), these two redox-isomeric copper species are shown to be in equilibrium, which depends on both temperature and solvent. For L(4)SSL(4) the μ-thiolate species forms as the kinetic product and further evolves into the disulfide complex under thermodynamic control, which creates the unprecedented possibility to compare both species under the same reaction conditions. The energies of the μ-thiolate and disulfide complexes for two series of related ligands have been calculated with DFT; the results rationalize the experimentally observed structures, and emphasize the important role that steric requirements play in the formation of the Cu(II) thiolate structure.
More Related Videos
11:38Quantifying the Binding Interactions Between CuII and Peptide Residues in the Presence and Absence of Chromophores
Published on: April 5, 2022
04:09Demonstrating the Simplicity and In Situ Temperature Monitoring of the Mechanochemical Synthesis of Metal Chalcogenides Suitable for Thermoelectrics
Published on: August 30, 2024
Related Concept Videos
Preparation and Reactions of Thiols
Formation of Complex Ions
The Equilibrium Constant
Calculating the Equilibrium Constant
For example, gaseous nitrogen dioxide forms dinitrogen tetroxide according to this equation:
Ladder Diagrams: Redox Equilibria
Consider the Fe3+/Fe2+ half-reaction, which has a standard-state potential of +0.771 V. At potentials more positive than +0.771 V, Fe3+ predominates, whereas Fe2+...
Free Energy Changes for Nonstandard States