Thermodynamics of the CuII μ-Thiolate and CuI Disulfide Equilibrium: A Combined Experimental and Theoretical Study

Erica C. M. Ording-Wenker, Martijn van der Plas, Maxime A. Siegler, Sylvestre Bonnet, F. Matthias Bickelhaupt, Celia Fonseca Guerra, Elisabeth Bouwman

Research output: Contribution to JournalArticleAcademicpeer-review


The redox equilibrium between dinuclear CuII
μ-thiolate and CuI disulfide structures has been analyzed
experimentally and via DFT calculations. Two new ligands,
L2SSL2 and L4SSL4, and their CuII μ-thiolate and CuI disulfide
complexes were synthesized. For L2SSL2, these two redoxisomeric
copper species are shown to be in equilibrium, which
depends on both temperature and solvent. For L4SSL4 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 CuII thiolate structure.
Original languageEnglish
Pages (from-to)8494-8504
Number of pages11
JournalInorganic Chemistry
Issue number16
Publication statusPublished - 4 Aug 2014


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