Isomerism in Molecular Metal Carbonyl Clusters

The present microreview focuses on different typologies of isomerism documented along the years for metal carbonyl clusters (MCCs), and outlines their analogies to other classes of ligand‐protected molecular clusters and nanoclusters. Isomerism in molecular MCCs is discussed within two main categories, that is, surface isomerism and core isomerism. The first Section presents some representative examples of surface isomerism involving inorganic (carbonyls and hydrides) and organic ligands, as well as isomerism due to ML fragments decorating the cluster surface. The second Section focuses on three major categories of core isomerism, that is: (1) isomers that mainly differ on M‐M distances; (2) isomers displaying different structures of the metal kernels; (3) isomers possessing almost identical metal kernels and ligand shells, but differing for the positions of different types of metal atoms within the metal kernel. The third Section briefly discusses two related and very rare cases of isomerism, that is, polymerisation and coordination isomerism. General conclusions are outlined in the final Section.