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Dithiocarbamates (R2CNS2 −) are a versatile class of monoanionic 1,1-dithio ligands and as they are easily prepared, a wide range of chemistry has been developed around them. This comprehensive review with over 2000 references covers their transition metal chemistry over the past 25 years. It begins with an overview of the ligands themselves, followed by a detailed general discussion of their transition metal complexes. This includes an overview of the synthetic methods adopted, their binding modes, ligand characteristics and spectroscopic properties, together with an analysis of structural studies and thermochemical data. The bulk of the review consists of a group survey of each transition metal element. These are further sub-sectioned allowing the reader easy access to the detailed aspects of the chemistry of each complex type. Each section also contains an account of already developed and future possible applications of the dithiocarbamate complexes. While the bulk of the review deals with the role of dithiocarbamates as versatile ancillary ligands, the final section considers their increasing prevalent non-innocent behavior. This comprehensive review is a must have for workers in this area.