Isolated Co‐Ti‐Y Trimetallic Synergistic Catalysis Based on Apparent Anti‐Electronegative Polarization

Rational design of multimetallic synergistic catalysis is a grand challenge in the field of green catalysis because synergistic mechanisms are poorly understood. Here, by exploiting a unique apparent anti‐electronegativity polarization in cobalt‐titanium‐yttrium trimetallic synergy, a unified methodology is demonstrated to activate oxygen and nitrogen. The new trimetallic synergistic catalyst achieves direct solvent‐free aerobic oxidation of cyclohexane to adipic acid and direct nitrogen oxidation of acetonitrile to guanidine. The delocalization of d‐orbitals and activation of inner electrons are the linchpins of catalytic performance, contributing to 90.87% selectivity for ketone‐alcohol oil and adipic‐acid and 89.30% selectivity for guanidine, respectively. The experiments and calculations demonstrate that the prodigious electrophilicity of the yttrium site overcomes the homeostasis of valence shell structures in the isolated cobalt and titanium sites. The valence electrons of this synergistic system become enriched with anti‐electronegative polarization and concomitant high charge transfer efficiency. In response to urging sustainable chemistry, the results corroborate that the activation strategies and mechanisms of molecular oxygen and nitrogen can be moderated and unified when multimetallic synergy is considered. A novel isolated trimetallic synergistic catalyst CoTiYAPO‐5 is designed and prepared. The spillover of inner electrons and delocalization of d‐orbitals are the keys to the outstanding catalytic activity. Exposed with CoTiYAPO‐5, direct solvent‐free aerobic oxidation of cyclohexane to adipic acid and direct nitrogen oxidation of acetonitrile to guanidine are achieved by sharing the same activation mechanism.