Gas-phase reactions driven by polarized metal-metal bonding in atomic clusters

Multimetallic catalysts exhibit great potential in the activation and catalytic transformation of small molecules. The polarized metal-metal bonds have been gradually recognized to account for the reactivity of multimetallic catalysts due to the synergistic effect of different metal centers. Gas-phase reactions on atomic clusters that compositionally resemble the active sites on related condensed-phase catalysts provide a widely accepted strategy to clarify the nature of polarized metal-metal bonds and the mechanistic details of elementary steps involved in the catalysis driven by this unique chemical bonding. This perspective review concerns the progress in the fundamental understanding of industrially and environmentally important reactions that are closely related to the polarized metal-metal bonds in clusters at a strictly molecular level. The following topics have been summarized and discussed: (1) catalytic CO oxidation with O₂, H₂O, and NO as oxidants (2) and the activation of other inert molecules (e.g., CH₄, CO₂, and N₂) mediated with clusters featuring polarized metal-metal bonding. It turns out that the findings in the gas phase parallel the catalytic behaviors of condensed-phase catalysts and the knowledge can prove to be essential in inspiring future design of promising catalysts.