Benzene and Its Derivatives as Bridging Ligands in Transition‐Metal Complexes

Transition‐metal complexes in which two or more metal atoms are bridged by one or more arene ligands led a shadowy existence in comparison to the extensive class of mononuclear arene complexes. Arene bridges can occur in a variety of coordination modes and with almost all of the transition–metal elements of the periodic table. Nowhere else are found so many forms of distorted and bent arene rings. The binuclear compounds can be divided into two classes: adducts which show relatively weak metal–arene bonding and complexes which show strong arene–metal interaction. Most of the adducts are in equilibrium with mononuclear complexes in solution or are only stable in the solid state (often as polymers). In both classes syn and anti coordination occurs; their geometries show a wide variation between the extreme cases of η 1 : η 1 ‐bridge and η 6 : η 6 ‐triple‐decker structure. Metal surfaces with chemisorbed arenes can be seen as a form of multinuclear arene–metal complexes. On transition‐metal surfaces, benzene can be bonded to one, two, or four surface atoms. Molecular clusters with face‐capping arene ligands that are bonded to three metal atoms have until now mainly been limited to two classes. The arenes bound to {(CO) 3 M} 3 (M = Ru, Os) or (CpCo) 3 clusters as μ 3 ‐η 2 : η 2 : η 2 ligands show only a weak trigonal distortion towards a Kekulé structure. Detailed investigations of the molecular structure and ligand dynamics of [(CpCo) 3 (μ 3 ‐arene)] complexes considerably help the understanding of the bonding of arenes to metal clusters and to metal surfaces.