Martínez-Vivas Sebastián, Poyatos Macarena, Peris Eduardo
Institute of Advanced Materials (INAM)., Universitat Jaume I, Av. Vicente Sos Baynat s/n., 12071, Castellón, Spain.
Angew Chem Int Ed Engl. 2023 Aug 21;62(34):e202307198. doi: 10.1002/anie.202307198. Epub 2023 Jul 12.
H 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 CH Cl . The interaction between coronene and the planar Rh complex is established by means of π-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 ν(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.
使用具有式[Rh(CNC)(CO)]的吡啶 - 二咪唑亚基钳形配体的阳离子配合物进行的¹H NMR研究表明，该化合物在CH₂Cl₂中与蔻具有高结合亲和力。蔻与平面Rh配合物之间的相互作用是通过π - 堆积相互作用建立的。这种相互作用对钳形CNC配体的给电子强度有强烈影响，如ν(CO)伸缩带向低频移动所示，其给电子强度显著增加。加入蔻会提高甲基碘对铑（I）钳形配合物亲核进攻的反应速率，并且对该配合物作为4 - 戊炔酸环异构化催化剂的性能也有积极影响。这些发现突出了超分子相互作用对于调节平面正方形金属配合物的反应性和催化活性的重要性。
