Synthesis of Transition Metal Dithiolenes

This chapter covers the major methods for the synthesis of transition metal dithiolene complexes, including the underpinning ligand chemistry. One broad class of methods are based on organosulfur chemistry leading to alkenedithiolates or their equivalents followed by complexation of these anions. A second broad approach involves formation of the dithiolene via reactions of coordinated ligands, such as the addition of alkynes to metal sulfido complexes. Methods leading to topical dithiolene complexes are described, including tetrathiaoxalate derivatives, tetrathiafulvalene (TTF) derived dithiolenes, linked bis(arenedithiol)s, and models for moybdopterin enzyme active sites.