Fig. 1: Schemes to map the active center and the dynamic evolution of hemilabile coordination.

Multiple techniques such as in situ XAFS and FT-IR combined with Solid-state NMR to unravel the reaction mechanism of propylene hydroformylation, from accurate identification to dynamic evolution of the active center during the reaction process over Rh–POPs catalysts. Direct experimental observation revealed how hemilabile PPh3-frame ligands dissociate and re-coordinate accompany the propylene reaction and desorption, then influence the regioselectivity in heterogeneous propylene hydroformylation.