Applications of Tripodal [S(3)] and [Se(3)] L(2)X Donor Ligands to Zinc, Cadmium and Mercury Chemistry: Organometallic and Bioinorganic Perspectives.

Abstract

The tripodal tris(2-mercapto-1-R-imidazolyl)hydroborato ligand system, [Tm(R)], and its selenium counterpart, [Tse(R)], provide useful platforms for investigating organometallic and bioinorganic aspects of the chemistry of zinc, cadmium and mercury in sulfur-rich and selenium-rich coordination environments. For example, the tridentate [Tm(R)] ligand provides an [S(3)] donor array that is of use for mimicking aspects of zinc enzymes and proteins that have sulfur-rich active sites, such as the Ada DNA repair protein. With respect to mercury, an interesting application of the [Tm(Bu(t) )] ligand is the synthesis of the mercury alkyl compounds [Tm(Bu(t) )]HgR (R = Me, Et) that react with PhSH to yield [Tm(Bu(t) )]HgSPh and RH, a reaction that emulates mercury detoxification by the organomercurial lyase, MerB. In addition to the tridentate [Tm(R)] and [Tse(R)] ligands, applications of the bidentate counterparts, [Bm(R)] and [Bse(R)] are also described.