Abstract
π-Coordination of aromatic molecules to metals dramatically alters their reactivity. For example, coordinated carbons become more electrophilic and C-H bonds of coordinated rings become more acidic. For many years, this change in reactivity has been used to trigger reactions that would not take place for uncoordinated arenes, however, there has been a recent resurgence in use of this technique, in part due to the development of catalytic reactions in which π-coordination is transient. In this Minireview, we describe the key reaction chemistry of arenes coordinated to a range of transition metals, including stereoselective reactions and industrially relevant syntheses. We also summarise outstanding examples of catalytic processes. Finally, we give perspectives on the future direction of the field, with respect to both reactions that are stoichiometric in activating metals and those employing catalytic metal.