Interest in the biomimetic properties of soft scorpionates based on methimazole commenced shortly after the reported synthesis of the hydrotris(methimazolyl)borate anion (TmMe) in 1996. These ligands are thione based and are thus not subject to facile oxidation and disulfide formation (c.f. thiolates). This allows these species to participate in an extensive coordination chemistry with a wide variety of metals. This review focuses on the chemistry of the RTmR and RBmR ligands with special reference to their use in biomimetic chemistry (alcohol dehydrogenase, Ada repair proteins, 5- aminolevulinate dehydratase, sulfite oxidase, hydrogenase, MerB) and their emerging use as radiopharmaceuticals (rhenium, technetium).