Heterometallic Coordination Compounds with Amino‐Acid Dithiocarbamate Ligands

Abstract Dithiocarbamates derived from amino acids (AA‐DTCs) are synthetically easily available O,S‐ditopic ligands that are potentially able to coordinate to a hard, oxophilic and to a soft, thiophilic metal site selectively, making them suitable as building blocks for heterobimetallic coordination compounds. When an AA‐DTC anion is treated with a transition metal ion (M1), usually a sulfur‐coordinate complex of defined geometry is formed widely uninfluenced by the oxygen functional group. The carboxylate group is capable to bind a second metal M2, where the carboxylate‐M2 linkage has a more ionic character and the coordination around M2 is characterized by carboxylate/solvent competition. In the vast majority of known compounds, the building blocks are linked into infinite assemblies of different dimensions. This comprehensive review surveys the synthesis and molecular structures of heterobimetallic compounds with AA‐DTC anions, comprising different salt‐like compounds of the highly oxophilic closed‐shell metal ions of groups 1–3, coordination polymers and networks for the first‐row transition metal ions, as well as highly covalent compounds with p‐block metal fragments as the oxophilic component.