The chemistry of the hydrotris(mercaptobenzothiazolyl)borate anion (Tbz) with metal salts (HgI2, SbI3, BiI3, CoCl2) is reported in an attempt to probe the stability of the of Tbz ligand once coordinated to hard and soft metals. Complexes of Tbz with bismuth, containing the [Bi(Tbz)I-3](-) anion, are stable, but with the other metals this is not the case. Although simple complexes such as [Hg(Tbz)I] and [E(Tbz)I-3](-) (E = Sb, Bi) can be isolated from the reaction mixtures, subsequent reactions lead to ligand modification or decomposition. In the presence of mercury and antimony we observe the formation of a hitherto unseen cationic pentacyclic heterocycle. With cobalt we observe a small quantity of a product which suggests a more complete decomposition. A simple benzothiazole (bz) adduct [Co(bz)(2)Cl-2] has been identified, in which the Tbz ligand has disintegrated and the parent heterocycle, mercaptobenzothiazole, has been desulfiirized. A rationale for these observations is given.