On-Demand Metal-to-Metal Electron Donation during Zr–Ru Heterodinuclear-Catalyzed Amine–Borane Dehydrogenation

Dinuclear metal–metal cooperative effects are important in catalysis involving the activation of small molecules with strong bonds. Here, we report density functional theory calculations used to determine the catalytic mechanism and metal–metal cooperative effects during amine–borane dehydrogenation catalyzed by a Zr–Ru heterodinuclear complex. These calculations revealed that, during catalysis bond activation, steps occur mainly at the Zr center and the Ru metal plays a role as a ligand-like on-demand electron donation partner. We also used calculations to determine the mechanistic and reactivity differences between the dinuclear Zr–Ru complex and mononuclear Zr and Ru complexes.