Wang Qiuran, Murphy Ryan P, Gau Michael R, Carroll Patrick J, Tomson Neil C
Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States.
Inorg Chem. 2024 Sep 30;63(39):18332-18344. doi: 10.1021/acs.inorgchem.4c02416. Epub 2024 Sep 18.
The use of a nonrigid, pyridyldialdimine-derived macrocyclic ligand (PDAI) enabled the synthesis of well-defined mono-, di-, tri-, and tetra-nuclear Cu(I) complexes in good yields through rational synthetic means. Starting from mono- and diargentous PDAI complexes, transmetalation to Cu(I) proceeded smoothly with formation of AgX (X = Cl, I) salts to generate mono-, di-, and trinuclear copper complexes. Monodentate supporting ligands (MeCN, xylNC, PMe, PPh) were found to either transmetallate with or bind various di- and trinuclear clusters. The solution-phase dynamic behaviors of these species were studied through NMR spectroscopic investigations, and an in-depth study of the trinuclear systems revealed a rate dependence on the identity of the supporting ligand, indicating that ligand dissociation reactions were involved in the dynamic exchange processes. Synthetic investigations further found methods for the purposeful interconversion between the di- and trinuclear systems as well as the synthesis of a pseudotetrahedral tetracopper complex with two μ-Ph supporting ligands.
使用一种非刚性的、吡啶二醛衍生的大环配体（PDAI），通过合理的合成方法能够以良好的产率合成结构明确的单核、双核、三核和四核Cu(I)配合物。从单银和双银PDAI配合物出发，与Cu(I)的金属转移反应顺利进行，同时形成AgX（X = Cl、I）盐，从而生成单核、双核和三核铜配合物。发现单齿配位配体（MeCN、二甲苯腈、PMe、PPh）要么发生金属转移反应，要么与各种双核和三核簇结合。通过核磁共振光谱研究对这些物种的溶液相动力学行为进行了研究，对三核体系的深入研究表明，反应速率取决于配位配体的种类，这表明配体解离反应参与了动态交换过程。合成研究进一步找到了在双核和三核体系之间进行有目的相互转化的方法，以及合成具有两个μ-Ph配位配体的假四面体四铜配合物的方法。
