The discovery of decamethyldizincocene [Zn(2)(η(5)-Cp*)(2)] (Cp* = C(5)Me(5)), the first complex containing a covalent zinc-zinc bond, by Carmona in 2004 initiated the search for this remarkable class of compounds. Low-valent organozinc complexes can either be formed by ligand substitution reactions of [Zn(2)(η(5)-Cp*)(2)] or by reductive coupling reactions of Zn(ii) compounds. To the best of our knowledge, until now 25 low-valent Zn-Zn bonded molecular compounds stabilized by a variety of sterically demanding, very often chelating, organic ligands have been synthesized and characterized. There are two major reaction pathways of [Zn(2)(η(5)-Cp*)(2)]: it can either react with cleavage of the Zn-Zn bond or by ligand substitution. In addition, upon reaction with late transition metal complexes, [Zn(2)(η(5)-Cp*)(2)] was found to form novel intermetallic complexes with Cp*Zn and Cp*Zn(2) acting as unusual one-electron donor ligands. Very recently, the potential capability of [Zn(2)(η(5)-Cp*)(2)] to serve as a suitable catalyst in hydroamination reactions was demonstrated. Finally, the recent work on Cd-Cd bonded coordination compounds is reviewed.