Lego-Inspired Ionic Polymer Catalysts Enabling Orthogonal Tandem Hydroformylation/Hydrogenation

Precisely engineering active sites while preventing cross-interference remains a critical challenge in heterogeneous orthogonal tandem catalysis. Herein, this work presents a Lego-inspired modular strategy for accurately engineering heterogeneous catalysts for the orthogonal tandem reaction. By employing [Rh/(SUL-Xantphos)]^2– and [(η⁵-Ph₄C₅)Ru(CO)₂Cl]⁻ anionic modules that incorporate into porous cationic polymers, respectively, two distinct catalysts (Rh/P-PIP and Ru–N-PIP) are synthesized. Rh/P-PIPs demonstrate exceptional regioselectivity in alkene hydroformylation (linear-to-branched ratio of aldehydes (l/b) up to 46.3). Meanwhile, Ru–N-PIPs exhibit efficient heptanal hydrogenation activity, performing alkene compatibility and CO tolerance. Leveraging the spatial isolation effect of polymer networks, mixing of Rh/P-PIPs and Ru–N-PIPs in appropriate proportions allows one-pot conversion of alkenes to alcohols with a 90.2% yield (l/b of alcohols up to 38.6), delivering efficient catalytic performance and broad substrate compatibility. Moreover, spatially arranging them in a fixed-bed reactor converts alkenes to alcohols with a selectivity of ∼70% with a l/b ratio of 23. This work establishes a Lego-modular strategy enabling efficient heterogeneous catalyst designs for orthogonal tandem reactions, where sequential reaction rates are balanced through catalyst ratio adjustment, creating a novel paradigm for designing and programming multicatalyst systems.