Adaptive Coordination Engineering for Efficient and Robust H 2 Release

ABSTRACT Efficient regulation of β‐H activation and its subsequent elimination remains a notorious challenge owing to stringent inherent geometric and electronic constraints. To overcome the high kinetic barriers, it necessitates a precise catalyst to effectively orchestrate the metal‐substrate interaction. Herein, we report a molecular Pd 1 ‐Ag 2 model using a tridentate phosphine ligand ( L2 ) and formate bridges, which integrates the effect of double silver synergy and nitrate anion regulation, and serves as the core origin to facilitate efficient β‐H elimination. Such bimetallic cooperation optimizes the reaction pathway and realizes rapid hydrogen production with complete CO‐free characteristics, endowing prominent industrial advantages over monometallic counterparts. Under ambient air at 60°C, this catalyst delivers excellent activity and satisfactory recyclability. DFT calculations confirm that the rate‐determining β‐H elimination step of monometallic Pd systems is effectively optimized, and in situ spectroscopic measurements further verify the stable proximal Pd‐Ag synergistic coordination throughout the reaction.