Dimerization in TMPA-Based Copper(I) Complexes: Implications for Redox Kinetics and Thermodynamics

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Abstract
Copper complexes of tris(2-pyridylmethyl)amine (TPA, TMPA, or TPMA) are widely studied for their redox activity and catalytic versatility. This study investigates solvent-dependent speciation of copper(I)-TMPA complexes, revealing a monomer-dimer equilibrium in solution. Using electrochemical analysis, variable-temperature NMR spectroscopy, and X-ray crystallography, we identify an embraced dimer with a lower reduction potential and faster electron transfer than the monomer. Notably, while the monomer displays strong solvent dependence, the dimer's redox properties remain largely invariant, reflecting its intrinsic stability.
Funding Information
  • Division of Chemistry (2340404)

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