Overriding the inherent alkalinity to dual phosphinito bimetallic catalyst for C(sp 2 )-C(sp 3 ) formation: A combined computational and experimental study

Unraveling the catalytic reaction mechanism is a long-term challenge for developing efficient catalysts. The blooming bimetallic catalyst have enabled to activate inert bonds and realize complex C-C formation. Herein, we theoretically discover a dual-phosphinito bridged hetero-bimetallic species that verified by NMR experiments. Our results indicate only dual-phosphinito Ni-Al model can be an active catalyst in asymmetric cycloadditions via C-C activation and C-H activation, which can well rationalize the experimental observations for both reactivity and stereo-selectivity. An unprecedented tandem redox dehydrogenation mechanism was revealed to control the formation of this active species overriding the inherent basicity. Synergistic Lewis acid and e g orbital interactions, including d z 2 orbital reoccupation and d x 2 -y 2 orbital recombination, were disclosed to understand both thermodynamic and kinetic advance of dual-bridged model, displaying feasible redox properties. & COPY; 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia