o-Dithiolene and o-aminothiolate chemistry of iron: Synthesis, structure and reactivity

Homoleptic complexes with an iron center bound by two o-dithiolene or o-aminothiolate ligands, or one tetradentate aminothiolate ligand will be discussed in the context of their molecular and electronic structures. These compounds are predominantly dimeric and exhibit rich redox chemistry due to the multiple redox active iron and ligand components. Their reaction with small molecules, namely, pyridines, amines, phosphines, phosphites, arsines, stibines, cyanide, halogens, and nitric oxide, has produced extensive libraries of compounds that are also reviewed. These five- and six-coordinate mononuclear and dinuclear adduct complexes access an incredibly broad range of iron and ligand spin and oxidation states that generates a multitude of electronic structures.