Cleaving Mercury-Alkyl Bonds: A Functional Model for Mercury Detoxification by MerB

The extreme toxicity of organomercury compounds that are found in the environment has focused attention on the mechanisms of action of bacterial remediating enzymes. We describe facile room-temperature protolytic cleavage by a thiol of the Hg-C bond in mercury-alkyl compounds that emulate the structure and function of the organomercurial lyase MerB. Specifically, the tris(2-mercapto-1-t-butylimidazolyl)hydroborato ligand [Tm(Bu(t))], which features three sulfur donors, has been used to synthesize [Tm(Bu(t))]HgR alkyl compounds (R = methyl or ethyl) that react with phenylthiol (PhSH) to yield [Tm(Bu(t))]HgSPh and RH. Although [Tm(Bu(t))]HgR compounds exist as linear two-coordinate complexes in the solid state, 1H nuclear magnetic resonance spectroscopy indicates that the complexes exist in rapid equilibrium with their higher-coordinate [kappa2-Tm(Bu(t))]HgR and [kappa3-Tm(Bu(t))]HgR isomers in solution. Facile access to a higher-coordinate species is proposed to account for the exceptional reactivity of [Tm(Bu(t))]HgR relative to that of other two-coordinate mercury-alkyl compounds.