Dimerization in TMPA-Based Copper(I) Complexes: Implications for Redox Kinetics and Thermodynamics
Marcos Tapia1, Shyam K Pahari1, Sandip Das1
1Department of Chemistry and Biochemistry, University of North Carolina at Greensboro, Greensboro, North Carolina 27402, United States.
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.
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