Tapia Marcos, Pahari Shyam K, Das Sandip, Khan Firoz Shah Tuglak, Hematian Shabnam
Department of Chemistry and Biochemistry, University of North Carolina at Greensboro, Greensboro, North Carolina 27402, United States.
Inorg Chem. 2025 Jun 30;64(25):12416-12422. doi: 10.1021/acs.inorgchem.5c01099. Epub 2025 Jun 16.
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.
三（2-吡啶甲基）胺（TPA、TMPA或TPMA）的铜配合物因其氧化还原活性和催化多功能性而受到广泛研究。本研究调查了铜（I）-TMPA配合物的溶剂依赖性物种形成，揭示了溶液中的单体-二聚体平衡。通过电化学分析、变温核磁共振光谱和X射线晶体学，我们鉴定出一种包合二聚体，其还原电位低于单体，电子转移速度比单体快。值得注意的是，虽然单体表现出强烈的溶剂依赖性，但二聚体的氧化还原性质基本保持不变，反映了其内在稳定性。
