Metal clusters in nature and artificial systems are known to exhibit excellent catalytic activities. Among various coordination systems, macrocyclic multinuclear metal complexes have unique structural features and great potential in organic synthesis. The multiple metal centers in a macrocyclic framework act as specific sites for the binding and activation of substrates, showing high catalytic activity and selectivity as a result of the cooperative effect of the multiple metal centers and robustness originating from macrocyclic skeletons. Most of them are precisely designed and synthesized, while occasionally, nice complexes also emerge from a fortuitous combination of metal ions and ligands. Here we overview the recent achievements of (i) multinuclear metal complexes with a covalently-linked macrocyclic ligand (category A), (ii) multinuclear metal complexes forming a macrocyclic skeleton (category B), and (iii) self-assembled supramolecular coordination complexes (category C). Various organic reactions catalyzed by these coordination systems are summarized here.
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