Jump to main content
Jump to site search

Issue 16, 2010
Previous Article Next Article

DFT studies of the degradation mechanism of methyl mercury activated by a sulfur-rich ligand

Author affiliations

Abstract

We describe theoretical insights into the mechanism of Hg–C bond protonolysis in methyl mercury coordinated by the tris(2-mercapto-1-tert-butylimidazolyl)hydroborato ligand, the structural and functional analogue of the organomercurial lyase MerB. Different cleavage pathways including both frontside and backside attack transition states were systematically studied by the hybrid density functional method B3LYP. Dependence of Hg–C bond activation on the primary sulfur coordination number of mercury was elaborated, and conceptual DFT indexes were suggested to be more appropriate than gross charge of atom sites in interpreting the dependence. Furthermore, absence of configurational inversion in MerB-catalyzed reactions was accounted for by examinations of the backside protonolysis pathways in the present system. Lastly, a rationalization was provided about the choice between different characteristics of transition states including both four-center and six-center ones.

Graphical abstract: DFT studies of the degradation mechanism of methyl mercury activated by a sulfur-rich ligand

Back to tab navigation

Supplementary files

Publication details

The article was received on 08 Sep 2009, accepted on 24 Dec 2009 and first published on 28 Jan 2010


Article type: Paper
DOI: 10.1039/B918402C
Citation: Phys. Chem. Chem. Phys., 2010,12, 3961-3971
  •   Request permissions

    DFT studies of the degradation mechanism of methyl mercury activated by a sulfur-rich ligand

    X. Li, R. Liao, W. Zhou and G. Chen, Phys. Chem. Chem. Phys., 2010, 12, 3961
    DOI: 10.1039/B918402C

Search articles by author

Spotlight

Advertisements