Heavier tetrylene- and tetrylyne-transition metal chemistry: it's no carbon copy.

Since the late 19th century, heavier tetrylene- and tetrylyne-transition metal chemistry has formed an important cornerstone in both main-group and organometallic chemistry alike. Driven by the success of carbene systems, significant efforts have gone towards the thorough understanding of the heavier group 14 derivatives, with examples now known from across the d-block. This now leads towards applications in cooperative bond activation, and moves ultimately towards well-defined catalytic systems. This review aims to summarise this vast field, from initial discoveries of tetrylene and tetrylyne complexes, to the most recent developments in reactivity and catalysis, as a platform to the future of this exciting, blossoming field.