Supramolecular Control of the Oxidative Addition as a Way To Improve the Catalytic Efficiency of Pincer-Rhodium (I) Complexes

H-1 NMR studies using a cationic complex with a pyridine-di-imidazolylidene pincer ligand of formula [Rh(CNC)(CO)](+) revealed that this compound showed high binding affinity with coronene in CH2Cl2. The interaction between coronene and the planar Rh-I complex is established by means of & pi;-stacking interactions. This interaction has a strong impact on the electron-donating strength of the pincer CNC ligand, which is increased significantly, as demonstrated by the shifting of the & nu;(CO) stretching bands to lower frequencies. The addition of coronene increases the reaction rate of the nucleophilic attack of methyl iodide on the rhodium (I) pincer complex, and also has a positive effect on the performance of the complex as a catalyst in the cycloisomerization of 4-pentynoic acid. These findings highlight the importance of supramolecular interactions for tuning the reactivity and catalytic activity of square-planar metal complexes.