Heteromultimetallic Platform for Enhanced C–H Bond Activation: Aluminum-Incorporated Dicopper Complex Mimicking Cu-ZSM-5 Structure and Oxidative Reactivity

Bimetallic complexes have sparked interest across various chemical disciplines, driving advancements in research. Recent advancements in this field have shed light on complex reactions in metalloenzymes and unveiled new chemical transformations. Two primary types of bimetallic platforms have emerged: (1) systems where both metals actively participate in reactivity, and (2) systems where one metal mediates the reaction while the other regulates reactivity. This study introduces a novel multinucleating ligand platform capable of integrating both types of bimetallic systems. To demonstrate the significance of this platform, we synthesized a unique dicopper complex incorporating aluminum in its coordination environment. This complex serves as the first structural model for the active site in copper-based zeolites, highlighting the role of aluminum in hydrogen atom abstraction reactivity. Comparative studies of oxidative C-H bond activation revealed that the inclusion of aluminum significantly alters the thermodynamic driving force (by -11 kcal mol^-1) for bond activation and modifies the proton-coupled electron-transfer reaction mechanism, resulting in a 14-fold rate increase. Both computational and experimental data support the high modularity of this multinucleating ligand platform, offering a new approach to fine-tune the reactivity of bimetallic complexes.